Graphene Oxide Nanosurface Reduces Apoptotic Death of HCT116 Colon Carcinoma Cells Induced by Zirconium Trisulfide Nanoribbons.

Due to their chemical, mechanical, and optical properties, 2D ultrathin nanomaterials have significant potential in biomedicine. However, the cytotoxicity of such materials, including their mutual increase or decrease, is still not well understood. We studied the effects that graphene oxide (GO) nanolayers (with dimensions 0.1-3 µm and average individual flake thickness less than 1 nm) and ZrS3 nanoribbons (length more than 10 µm, width 0.4-3 µm, and thickness 50-120 nm) have on the viability, cell cycle, and cell death of HCT116 colon carcinoma cells. We found that ZrS3 exhibited strong cytotoxicity by causing apoptotic cell death, which was in contrast to GO. When adding GO to ZrS3, ZrS3 was significantly less toxic, which may be because GO inhibits the effects of cytotoxic hydrogen sulfide produced by ZrS3. Thus, using zirconium trisulfide nanoribbons as an example, we have demonstrated the ability of graphene oxide to reduce the cytotoxicity of another nanomaterial, which may be of practical importance in biomedicine, including the development of biocompatible nanocoatings for scaffolds, theranostic nanostructures, and others.

The Conditions Matter: The Toxicity of Titanium Trisulfide Nanoribbons to Bacteria E. coli Changes Dramatically Depending on the Chemical Environment and the Storage Time.

In this work, we present an analysis of the antibacterial activity of TiS3 nanostructures in water and 0.9% NaCl solution suspensions. TiS3 nanoribbons 1-10 µm long, 100-300 nm wide, and less than 100 nm thick were produced by the direct reaction of pure titanium powder with elemental sulphur in a quartz tube sealed under vacuum. For the toxicity test of a bioluminescent strain of E. coli we used concentrations from 1 to 0.0001 g L-1 and also studied fresh suspensions and suspensions left for 24 h. The strongest toxic effect was observed in freshly prepared water solutions where the luminescence of bacteria decreased by more than 75%. When saline solution was substituted for water or when the solutions were stored for 24 h it resulted in a considerable decrease in the TiS3 antibacterial effect. The toxicity of TiS3 in water exceeded the toxicity of the reference TiO2 nanoparticles, though when saline solution was used instead of water the opposite results were observed. In addition, we did not find a relationship between the antibacterial activity of water suspensions of nanoribbons and the stability of their colloidal systems, which indicates an insignificant contribution to the toxicity of aggregation processes. In 0.9% NaCl solution suspensions, toxicity increased in proportion to the increase in the zeta potential. We suppose that the noted specificity of toxicity is associated with the emission of hydrogen sulphide molecules from the surface of nanoribbons, which, depending on the concentration, can either decrease or increase oxidative stress, which is considered the key mechanism of nanomaterial cytotoxicity. However, the exact underlying mechanisms need further investigation. Thus, we have shown an important role of the dispersion medium and the period of storage in the antibacterial activity of TiS3 nanoribbons. Our results could be used in nanotoxicological studies of other two-dimensional nanomaterials, and for the development of novel antibacterial substances and other biomedical applications of this two-dimensional material.

Chemical vapor deposition and characterization of two-dimensional molybdenum dioxide (MoO2) nanoplatelets.

We report on the chemical vapor deposition synthesis of MoO2 nanoplatelets by sublimation of MoO3 and its reduction in a hydrogen atmosphere at 750 °C. When grown on Si/SiO2 substrates, the platelets primarily assume a rhomboidal shape and have thicknesses ranging from several to tens of nm. The morphology of MoO2 crystals was found to depend on the chemical nature of substrates. MoO2 platelets on Si/SiO2 were characterized by a number of microscopic and spectroscopic techniques, and the electrical measurements revealed the metallic nature of their conductivity averaging at 2400 ± 1000 S cm-1. Raman spectroscopy of MoO2 platelets on graphene indicates their strong hole injection property. Small thickness, planar morphology, high chemical stability and metallic conductivity of ultrathin MoO2 platelets make them potentially interesting for integration different other two-dimensional materials in a variety of electronic structures and devices.

Nanotoxicity of ZrS3 Probed in a Bioluminescence Test on E. coli Bacteria: The Effect of Evolving H2S.

Materials from a large family of transition metal trichalcogenides (TMTCs) attract considerable attention because of their potential applications in electronics, optoelectronics and energy storage, but information on their toxicity is lacking. In this study, we investigated the toxicity of ZrS3, a prominent TMTC material, toward photoluminescent E. coli bacteria in a bioluminescence test. We found that freshly prepared ZrS3 suspensions in physiological saline solution with concentrations as high as 1 g/L did not exhibit any toxic effects on the bacteria. However, ZrS3 suspensions that were stored for 24 h prior to the bioluminescence tests were very toxic to the bacteria and inhibited their emission, even at concentrations down to 0.001 g/L. We explain these observations by the aqueous hydrolysis of ZrS3, which resulted in the formation of ZrOx on the surface of ZrS3 particles and the release of toxic H2S. The formation of ZrOx was confirmed by the XPS analysis, while the characteristic H2S smell was noticeable for the 24 h suspensions. This study demonstrates that while ZrS3 appears to be intrinsically nontoxic to photoluminescent E. coli bacteria, it may exhibit high toxicity in aqueous media. The results of this study can likely be extended to other transition metal chalcogenides, as their toxicity in aqueous solutions may also increase over time due to hydrolysis and the formation of H2S. The results of this study also demonstrate that since many systems involving nanomaterials are unstable and evolve over time in various ways, their toxicity may evolve as well, which should be considered for relevant toxicity tests.

Effect of GO on bacterial cells: Role of the medium type and electrostatic interactions.

Graphene and graphene oxide (GO) both being two-dimensional materials are gaining popularity among researchers as a promising nanomaterial for various medical and biological applications. The aim of this study is to elucidate the influence of nanostructured GO sheets on viability of a model species of gram-negative E. coli bacteria transformed with pRSET-emGFP plasmid in in vitro experiments. It was shown that GO at concentrations between 0.0025 and 2.5 g/l in growth medium inhibits growth of bacterial colonies, while in physiological saline solution (PS) this effect decreases dramatically to the point of complete disappearance. It was shown that in order to obtain a pronounced antibacterial effect one needs to introduce high concentrations of GO into the media (up to 2.5 g/l), which can be important for development of antibacterial materials for biomedical applications. Some of the obtained data provide clear evidence to electrostatic nature of interaction between bacterial and GO sheets. A number of previous papers suggested the process of biofilms formation by bacteria as the primary reason for aggregation between graphene-like materials and bacterial cells. However, formation of flocculent structures consisting of GO and dead bacteria and accompanied with decrease in zeta-potential of particles in the suspension to 18 mV proves that electrostatic interactions play the major role in aggregation. The obtained data can be used for employing GO and similar materials in new systems for water-purification from biological contaminants. Besides, our results stress the importance of accounting for the conditions in which goods and coatings containing graphene-like materials as an antibacterial agent are used, as well as unification of the experimental conditions.

Medium-Dependent Antibacterial Properties and Bacterial Filtration Ability of Reduced Graphene Oxide.

Toxicity of reduced graphene oxide (rGO) has been a topic of multiple studies and was shown to depend on a variety of characteristics of rGO and biological objects of interest. In this paper, we demonstrate that when studying the same dispersions of rGO and fluorescent Escherichia coli (E. coli) bacteria, the outcome of nanotoxicity experiments also depends on the type of culture medium. We show that rGO inhibits the growth of bacteria in a nutrition medium but shows little effect on the behavior of E. coli in a physiological saline solution. The observed effects of rGO on E. coli in different media could be at least partially rationalized through the adsorption of bacteria and nutrients on the dispersed rGO sheets, which is likely mediated via hydrogen bonding. We also found that the interaction between rGO and E. coli is medium-dependent, and in physiological saline solutions they form stable flocculate structures that were not observed in nutrition media. Furthermore, the aggregation of rGO and E. coli in saline media was observed regardless of whether the bacteria were alive or dead. Filtration of the aggregate suspensions led to nearly complete removal of bacteria from filtered liquids, which highlights the potential of rGO for the filtration and separation of biological contaminants, regardless of whether they include live or dead microorganisms.

Slot-Die-Printed Two-Dimensional ZrS3 Charge Transport Layer for Perovskite Light-Emitting Diodes.

Liquid-phase exfoliation of zirconium trisulfide (ZrS3) was used to produce stable and ready-to-use inks for solution-processed semiconductor thin-film deposition. Ribbon-like layered crystals of ZrS3 were produced by the chemical vapor transport method and were then exfoliated in three different solvents: dimethylformamide, ethanol, and isopropyl alcohol. The resulting ZrS3 dispersions were compared for stability and the ability to form continuous films on top of the perovskite layer in light-emitting diodes with the ITO/PEDOT:PSS/MAPbBr3/2D-ZrS3/LiF/Al structure. Film deposition was performed by using either spray or slot-die coating methods. The slot-die coating route proved to produce better and more uniform films with respect to spray coating. We found that the 2D ZrS3 electron injection layer (EIL) stabilized the interface between the perovskite and LiF/Al cathode, reducing the turn-on voltage to 2.8 V and showing a luminance that does not degrade during voltage sweep. On the other hand, EIL-free devices show electroluminescence on the first voltage sweep that reduces almost to zero in the subsequent sweeps. Combining physical device simulation and density functional theory calculation, we are able to explain these results in terms of lowering the electron injection barrier at the cathode.

Quasi-1D TiS3 Nanoribbons: Mechanical Exfoliation and Thickness-Dependent Raman Spectroscopy.

Quasi-one-dimensional (quasi-1D) materials enjoy growing interest due to their unusual physical properties and promise for miniature electronic devices. However, the mechanical exfoliation of quasi-1D materials into thin flakes and nanoribbons received considerably less attention from researchers than the exfoliation of conventional layered crystals. In this study, we investigated the micromechanical exfoliation of representative quasi-1D crystals, TiS3 whiskers, and demonstrate that they typically split into narrow nanoribbons with very smooth, straight edges and clear signatures of 1D TiS3 chains. Theoretical calculations show that the energies required for breaking weak interactions between the two-dimensional (2D) layers and between 1D chains within the layers are comparable and, in turn, are considerably lower than those required for breaking the covalent bonds within the chains. We also emulated macroscopic exfoliation experiments on the nanoscale by applying a local shear force to TiS3 crystals in different crystallographic directions using a tip of an atomic force microscopy (AFM) probe. In the AFM experiments, it was possible to slide the 2D TiS3 layers relative to each other as well as to remove selected 1D chains from the layers. We systematically studied the exfoliated TiS3 crystals by Raman spectroscopy and identified the Raman peaks whose spectral positions were most dependent on the crystals' thickness. These results could be used to distinguish between TiS3 crystals with thickness ranging from one to about seven monolayers. The conclusions established in this study for the exfoliated TiS3 crystals can be extended to a variety of transition metal trichalcogenide materials as well as other quasi-1D crystals. The possibility of exfoliation of TiS3 into narrow (few-nm wide) crystals with smooth edges could be important for the future realization of miniature device channels with reduced edge scattering of charge carriers.