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.

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.

Synthesis, Toxicity Assessment, Environmental and Biomedical Applications of MXenes: A Review.

MXenes are a family of two-dimensional (2D) composite materials based on transition metal carbides, nitrides and carbonitrides that have been attracting attention since 2011. Combination of electrical and mechanical properties with hydrophilicity makes them promising materials for biomedical applications. This review briefly discusses methods for the synthesis of MXenes, their potential applications in medicine, ranging from sensors and antibacterial agents to targeted drug delivery, cancer photo/chemotherapy, tissue engineering, bioimaging, and environmental applications such as sensors and adsorbents. We focus on in vitro and in vivo toxicity and possible mechanisms. We discuss the toxicity analogies of MXenes and other 2D materials such as graphene, mentioning the greater biocompatibility of MXenes. We identify existing barriers that hinder the formation of objective knowledge about the toxicity of MXenes. The most important of these barriers are the differences in the methods of synthesis of MXenes, their composition and structure, including the level of oxidation, the number of layers and flake size; functionalization, test concentrations, duration of exposure, and individual characteristics of biological test objects Finally, we discuss key areas for further research that need to involve new methods of nanotoxicology, including predictive computational methods. Such studies will bring closer the prospect of widespread industrial production and safe use of MXene-based products.

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.

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.

Author Correction: Titanium-carbide MXenes for work function and interface engineering in perovskite solar cells.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

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.

Titanium-carbide MXenes for work function and interface engineering in perovskite solar cells.

To improve the efficiency of perovskite solar cells, careful device design and tailored interface engineering are needed to enhance optoelectronic properties and the charge extraction process at the selective electrodes. Here, we use two-dimensional transition metal carbides (MXene Ti3C2Tx) with various termination groups (Tx) to tune the work function (WF) of the perovskite absorber and the TiO2 electron transport layer (ETL), and to engineer the perovskite/ETL interface. Ultraviolet photoemission spectroscopy measurements and density functional theory calculations show that the addition of Ti3C2Tx to halide perovskite and TiO2 layers permits the tuning of the materials' WFs without affecting other electronic properties. Moreover, the dipole induced by the Ti3C2Tx at the perovskite/ETL interface can be used to change the band alignment between these layers. The combined action of WF tuning and interface engineering can lead to substantial performance improvements in MXene-modified perovskite solar cells, as shown by the 26% increase of power conversion efficiency and hysteresis reduction with respect to reference cells without MXene.

Decoupled in-plane Dipole Resonance Modulated Colorimetric Assay-Based Optical Ruler for Ultra-Trace Gold (Au) Detection.

Decoupling of different plasmon resonance modes (in-plane, and out-of-plane dipole and quadrupole resonances) by tuning nanoparticle's size and shape offers a new field of plasmonics as colorimetric assay-based optical-ruler for ultra-trace sensing. Driven by its low cost, easy to perform and efficient way to measure trace level (up to 30 ppt in presence of common mining elements in natural gold ore) abundance, this study develops a highly selective and ultrasensitive turn-on colorimetric sensor to detect gold-ion from environmental samples. Different level of gold-ion tracer makes size variable spherical- and disc-shaped silver nanoparticles when added to a 'growth solution' which results decoupling of in-plane dipole resonance from in-plane quadrupole and out-of-plane dipole resonances with a wide range of in-plane dipole plasmon tunability to generate different colors. This color-coded sensing of gold-ion shows high selectivity and ultrasensitivity over other metal ions in the ppt level with an impurity aberration limit of 1 ppm. A plausible explanation explains the possible role of catalytic gold-ion to initiate unfavorable silver ion (Ag+) reduction by ascorbic acid to generate silver nanoparticles. Proposed technology has been applied in real mining sample (Bugunda Gold Deposit, Tajikistan) to detect gold concentration from ores to find potential application in mining technology.

The Room-Temperature Chemiresistive Properties of Potassium Titanate Whiskers versus Organic Vapors.

The development of portable gas-sensing units implies a special care of their power efficiency, which is often approached by operation at room temperature. This issue primarily appeals to a choice of suitable materials whose functional properties are sensitive toward gas vapors at these conditions. While the gas sensitivity is nowadays advanced by employing the materials at nano-dimensional domain, the room temperature operation might be targeted via the application of layered solid-state electrolytes, like titanates. Here, we report gas-sensitive properties of potassium titanate whiskers, which are placed over a multielectrode chip by drop casting from suspension to yield a matrix mono-layer of varied density. The material synthesis conditions are straightforward both to get stable single-crystalline quasi-one-dimensional whiskers with a great extent of potassium replacement and to favor the increase of specific surface area of the structures. The whisker layer is found to be sensitive towards volatile organic compounds (ethanol, isopropanol, acetone) in the mixture with air at room temperature. The vapor identification is obtained via processing the vector signal generated by sensor array of the multielectrode chip with the help of pattern recognition algorithms.

Polarization-Dependent Photoinduced Bias-Stress Effect in Single-Crystal Organic Field-Effect Transistors.

Photoinduced charge transfer between semiconductors and gate dielectrics can occur in organic field-effect transistors (OFETs) operating under illumination, leading to a pronounced bias-stress effect in devices that are normally stable while operating in the dark. Here, we report an observation of a polarization-dependent photoinduced bias-stress effect in two prototypical single-crystal OFETs, based on rubrene and tetraphenylbis(indolo{1,2-a})quinolin. We find that the decay rate of the source-drain current in these OFETs under illumination is a periodic function of the polarization angle of incident photoexcitation with respect to the crystal axes, with a periodicity of π. The angular positions of maxima and minima of the bias-stress rate match those of the optical absorption coefficient of the corresponding crystals. The analysis of the effect shows that it stems from a charge transfer of "hot" holes, photogenerated in the crystal within a very short thermalization length (≪µm) from the semiconductor-dielectric interface. The observed phenomenon is a type of intrinsic structure-property relationship, revealing how molecular packing affects parameter drift in organic transistors under illumination. We also demonstrate that a photoinduced charge transfer in OFETs can be used for recording rewritable accumulation channels with an optically defined geometry and resolution, which can be used in a number of potential applications.

Development of a Triplet-Triplet Absorption Ruler: DNA- and Chromatin-Mediated Drug Molecule Release from a Nanosurface.

Triplet-triplet (T-T) absorption spectroscopy has been used successfully as a molecular ruler to understand the actual release process of sanguinarine as a drug molecule from a gold nanoparticle surface in the presence of cell components, that is, DNA and chromatin. The obtained results have been verified by fluorescence and surface-enhanced Raman spectroscopy (SERS), and a plausible explanation has been put forward to describe the underestimation and overestimation of the percentage (%) of the release of drug molecules measured by fluorescence- and SERS-based techniques, respectively, over the highlighted T-T absorption spectroscopy. Because of the intrinsic nature of absorption, the reported T-T absorption spectroscopic assay overpowers fluorescence- and SERS-based assays, which are limited by the long-range interaction and nonlinear dependence of the concentration of analytes, respectively.

Considerable Variation of Antibacterial Activity of Cu Nanoparticles Suspensions Depending on the Storage Time, Dispersive Medium, and Particle Sizes.

Suspensions of Cu nanoparticles are promising for creating the new class of alternative antimicrobial products. In this study we examined copper nanoparticles of various sizes obtained by the method of wire electric explosion: nanopowder average size 50 nm (Cu 50) and 100 nm (Cu 100). The paper presents the complex study of the influence of physicochemical properties such as particle size and concentration of the freshly prepared and 24-hour suspensions of Cu nanoparticles in distilled water and physiological solution upon their toxicity to bacteria E. coli M-17. Ionic solution of Cu(2+) and sodium dichloroisocyanurate was used for comparison study. It has been shown that decrease in the nanoparticle size leads to changes in the correlation between toxicity and concentration as toxicity peaks are observed at low concentrations (0.0001⋯0.01 mg/L). It has been observed that antibacterial properties of Cu 50 nanoparticle suspensions are ceased after 24-hour storage, while for Cu 100 suspensions no correlation between antibacterial properties and storage time has been noted. Cu 100 nanoparticle suspensions at 10 mg/L concentration display higher toxicity at substituting physiological solution for water than Cu 50 suspensions. Dependence of the toxicity on the mean particle aggregates size in suspension was not revealed.