From Light to Dark: Dancing with Electrons in Colloidal 2D MoS2 Nanosheets.

Extending the lifetime of photogenerated electrons in semiconductor systems is an important criterion for the conversion of light into storable energy. We have now succeeded in storing electrons in a photoirradiated colloidal molybdenum disulfide (MoS2) suspension, showcasing its unique reversible photoresponsive behavior. The dampened A and B excitonic peaks indicate the accumulation of photogenerated electrons and the minimization of interactions between MoS2 interlayers. The stored electrons were quantitatively extracted by titrating with a ferrocenium ion in the dark, giving ca. 0.2 electrons per MoS2 formula unit. The emergence of the photoinduced A1g* Raman mode and the decrease in zeta potential after irradiation suggest intercalation of counterions to maintain overall charge balance upon electron storage. These results provide insights into the mechanism of photogenerated electron storage in 2D materials and pave the way for the potential application of colloidal 2D materials in electron storage.

Quantifying hydroxyl radicals generated by a low-temperature plasma using coumarin: methodology and precautions.

The detection and quantification of hydroxyl radicals (HO˙) generated by low-temperature plasmas (LTPs) are crucial for understanding their role in diverse applications of plasma radiation. In this study, the formation of HO˙ in the irradiated aqueous phase is investigated at various plasma parameters, by probing them indirectly using the coumarin molecule. We propose a quantification methodology for these radicals, combining spectrophotometry to study the coumarin reaction with hydroxyl radicals and fluorimetry to evaluate the formation yield of the hydroxylated product, 7-hydroxycoumarin. Additionally, we thoroughly examine and discuss the impact of pH on this quantification process. This approach enhances our comprehension of HO˙ formation during LTP irradiation, adding valuable insights to plasma's biological applications.

Direct Probing of Water Adsorption on Liquid-Phase Exfoliated WS2 Films Formed by the Langmuir-Schaefer Technique.

Tungsten disulfide, a transition metal dichalcogenide, has numerous applications as active components in gas- and chemical-sensing devices, photovoltaic sources, photocatalyst substrates, etc. In such devices, the presence of water in the sensing environment is a factor whose role has not been well-understood. To address this problem, the in situ probing of H2O molecule adsorption on WS2 films supported on solid substrates has been performed in a near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) setup. Instead, on the individual nanoflakes or spray-coated samples, the measurements were performed on highly transparent, homogeneous, thin films of WS2 nanosheets self-assembled at the interface of two immiscible liquids, water and toluene, transferred onto a solid substrate by the Langmuir-Schaefer technique. This experiment shows that edge defects in nanoflakes, tungsten dangling bond ensuing the exfoliation in the liquid phase, represent active sites for the WO3, WO3-x, and WO3·nH2O formation under ambient conditions. These oxides interact with water molecules when the WS2 films are exposed to water vapor in the NAP-XPS reaction cell. However, water molecules do not influence the W-S chemical bond, thus indicating the physisorption of H2O molecules at the WS2 film surface.

DNA Strand Breaks and Denaturation as Probes of Chemical Reactivity versus Thermal Effects of Atmospheric Pressure Plasma Jets.

An atmospheric pressure plasma jet (APPJ) is being advanced as an alternative radiation type that offers excellent efficacy in an array of medical applications against specific biological targets such as DNA. This work explores the possibility of implementing DNA and its damage as a probe for specific plasma diagnostics such as reactive plasma species formation and transient local heating. We analyzed both APPJ characteristics based on the detection of plasma-induced strand breaks and DNA denaturation. Further, we implemented a machine learning model based on artificial neural networks to predict the type and extent of DNA damage for a given combination of APPJ parameter values. This methodology is an important step toward deciphering and explaining the potential adverse effects of APPJ on biological samples of any prospective interest in medicine.

Revealing low-temperature plasma efficacy through a dose-rate assessment by DNA damage detection combined with machine learning models.

Low-temperature plasmas have quickly emerged as alternative and unconventional types of radiation that offer great promise for various clinical modalities. As with other types of radiation, the therapeutic efficacy and safety of low-temperature plasmas are ubiquitous concerns, and assessing their dose rates is crucial in clinical settings. Unfortunately, assessing the dose rates by standard dosimetric techniques has been challenging. To overcome this difficulty, we proposed a dose-rate assessment framework that combined the predictive modeling of plasma-induced damage in DNA by machine learning with existing radiation dose-DNA damage correlations. Our results indicated that low-temperature plasmas have a remarkably high dose rate that can be tuned by various process parameters. This attribute is beneficial for inducing radiobiological effects in a more controllable manner.

Electron ionization of clusters containing the formamide molecule.

Studies on electron interactions with formamide (FA) clusters promote scientific interest as a model system to understand phenomena relevant to astrophysical, prebiotic, and radiobiological processes. In this work, mass spectrometric detection of cationic species for both small bare and microhydrated formamide clusters was performed at an electron ionization of 70 eV. Furthermore, a comparative analysis of the cluster spectra with the literature-reported gas-phase spectra is presented and discussed, revealing different reaction channels affected by the cluster environment. This study is essential in developing our understanding of both low-energy electron phenomena in clusters that can bridge the complexity gap between gas and realistic systems and the effect of hydration on electron-induced processes.

Atmospheric Pressure Plasmas in Material Science.

The long-term goal of basic material research is to develop theoretical and experimental methodologies to advance the ability to produce materials with the desired compositions and properties that can be used in various applications [...].

Dissociative electron attachment to amide bond containing molecules: N-ethylformamide and N-ethylacetamide.

To advance our quest to understand the role of low energy electrons in biomolecular systems, we performed investigations on dissociative electron attachment (DEA) to gas-phase N-ethylformamide (NEF) and N-ethylacetamide (NEA) molecules. Both molecules contain the amide bond, which is the linkage between two consecutive amino acid residues in proteins. Thus, their electron-induced dissociation can imitate the resonant behavior of the DEA process in more complex biostructures. Our experimental results indicate that in these two molecules, the dissociation of the amide bond results in a double resonant structure with peaks at ∼5 eV and 9 eV. We also determined the energy position of resonant states for several negative ions, i.e., the other dissociation products from NEF and NEA. Our predictions of dissociation channels were supported by density functional theory calculations of the corresponding threshold energies. Our results and those previously reported for small amides and peptides imply the fundamental nature for breakage of the amide bond through the DEA process.

Atmospheric Pressure Plasma Deposition of TiO2: A Review.

Atmospheric pressure plasma (APP) deposition techniques are useful today because of their simplicity and their time and cost savings, particularly for growth of oxide films. Among the oxide materials, titanium dioxide (TiO2) has a wide range of applications in electronics, solar cells, and photocatalysis, which has made it an extremely popular research topic for decades. Here, we provide an overview of non-thermal APP deposition techniques for TiO2 thin film, some historical background, and some very recent findings and developments. First, we define non-thermal plasma, and then we describe the advantages of APP deposition. In addition, we explain the importance of TiO2 and then describe briefly the three deposition techniques used to date. We also compare the structural, electronic, and optical properties of TiO2 films deposited by different APP methods. Lastly, we examine the status of current research related to the effects of such deposition parameters as plasma power, feed gas, bias voltage, gas flow rate, and substrate temperature on the deposition rate, crystal phase, and other film properties. The examples given cover the most common APP deposition techniques for TiO2 growth to understand their advantages for specific applications. In addition, we discuss the important challenges that APP deposition is facing in this rapidly growing field.

Large-Scale Image Analysis for Investigating Spatio-Temporal Changes in Nuclear DNA Damage Caused by Nitrogen Atmospheric Pressure Plasma Jets.

The effective clinical application of atmospheric pressure plasma jet (APPJ) treatments requires a well-founded methodology that can describe the interactions between the plasma jet and a treated sample and the temporal and spatial changes that result from the treatment. In this study, we developed a large-scale image analysis method to identify the cell-cycle stage and quantify damage to nuclear DNA in single cells. The method was then tested and used to examine spatio-temporal distributions of nuclear DNA damage in two cell lines from the same anatomic location, namely the oral cavity, after treatment with a nitrogen APPJ. One cell line was malignant, and the other, nonmalignant. The results showed that DNA damage in cancer cells was maximized at the plasma jet treatment region, where the APPJ directly contacted the sample, and declined radially outward. As incubation continued, DNA damage in cancer cells decreased slightly over the first 4 h before rapidly decreasing by approximately 60% at 8 h post-treatment. In nonmalignant cells, no damage was observed within 1 h after treatment, but damage was detected 2 h after treatment. Notably, the damage was 5-fold less than that detected in irradiated cancer cells. Moreover, examining damage with respect to the cell cycle showed that S phase cells were more susceptible to DNA damage than either G1 or G2 phase cells. The proposed methodology for large-scale image analysis is not limited to APPJ post-treatment applications and can be utilized to evaluate biological samples affected by any type of radiation, and, more so, the cell-cycle classification can be used on any cell type with any nuclear DNA staining.

Irradiation-induced reactions at the CeO2/SiO2/Si interface.

The influence of high-energy (1.6 MeV) Ar2+ irradiation on the interfacial interaction between cerium oxide thin films (∼15 nm) with a SiO2/Si substrate is investigated using transmission electron microscopy, ultrahigh vacuum x-ray photoelectron spectroscopy (XPS), and a carbon monoxide (CO) oxidation catalytic reaction using ambient pressure XPS. The combination of these methods allows probing the dynamics of vacancy generation and its relation to chemical interactions at the CeO2/SiO2/Si interface. The results suggest that irradiation causes amorphization of some portion of CeO2 at the CeO2/SiO2/Si interface and creates oxygen vacancies due to the formation of Ce2O3 at room temperature. The subsequent ultra-high-vacuum annealing of irradiated films increases the concentration of Ce2O3 with the simultaneous growth of the SiO2 layer. Interactions with CO molecules result in an additional reduction of cerium and promote the transition of Ce2O3 to a silicate compound. Thermal annealing of thin films exposed to oxygen or carbon monoxide shows that the silicate phase is highly stabile even at 450 °C.

Dipole-Supported Electronic Resonances Mediate Electron-Induced Amide Bond Cleavage.

Dissociative electron attachment (DEA) plays a key role in radiation damage of biomolecules under high-energy radiation conditions. The initial step in DEA is often rationalized in terms of resonant electron capture into one of the metastable valence states of a molecule followed by its fragmentation. Our combined theoretical and experimental investigations indicate that the manifold of states responsible for electron capture in the DEA process can be dominated by core-excited (shake-up) dipole-supported resonances. Specifically, we present the results of experimental and computational studies of the gas-phase DEA to three prototypical peptide molecules, formamide, N-methylformamide (NMF), and N,N-dimethyl-formamide (DMF). In contrast to the case of electron capture by positively charged peptides in which amide bond rupture is rare compared to N─C_{α} bond cleavage, fragmentation of the amide bond was observed in each of these three molecules. The ion yield curves for ions resulting from this amide bond cleavage, such as NH_{2}^{-} for formamide, NHCH_{3}^{-} for NMF, and N(CH_{3})_{2}^{-} for DMF, showed a double-peak structure in the region between 5 and 8 eV. The peaks are assigned to Feshbach resonances including core-excited dipole-supported resonances populated upon electron attachment based on high-level electronic structure calculations. Moreover, the lower energy peak is attributed to formation of the core-excited resonance that correlates with the triplet state of the neutral molecule. The latter process highlights the role of optically spin-forbidden transitions promoted by electron impact in the DEA process.

Exfoliated Graphene Leads to Exceptional Mechanical Properties of Polymer Composite Films.

Polymers with superior mechanical properties are desirable in many applications. In this work, polyethylene (PE) films reinforced with exfoliated thermally reduced graphene oxide (TrGO) fabricated using a roll-to-roll hot-drawing process are shown to have outstanding mechanical properties. The specific ultimate tensile strength and Young's modulus of PE/TrGO films increased monotonically with the drawing ratio and TrGO filler fraction, reaching up to 3.2 ± 0.5 and 109.3 ± 12.7 GPa, respectively, with a drawing ratio of 60× and a very low TrGO weight fraction of 1%. These values represent by far the highest reported to date for a polymer/graphene composite. Experimental characterizations indicate that as the polymer films are drawn, TrGO fillers are exfoliated, which is further confirmed by molecular dynamics (MD) simulations. Exfoliation increases the specific area of the TrGO fillers in contact with the PE matrix molecules. Molecular dynamics simulations show that the PE-TrGO interaction is stronger than the PE-PE intermolecular van der Waals interaction, which enhances load transfer from PE to TrGO and leverages the ultrahigh mechanical properties of TrGO.

Total yield of reactive species originating from an atmospheric pressure plasma jet in real time.

It is now well established that plasma-induced reactive species are key agents involved in many biochemical reactions. This work reports on the formation of plasma reactive species in an acidified ferrous sulfate (Fricke) solution interacting with an atmospheric pressure plasma jet (APPJ). A yield of ferric (Fe3+) ions measured using in situ absorption spectroscopy was attributed to the formation of plasma reactive species provided and/or originated in the solution. The results indicated that the number of reactive species formed was proportional to plasma frequency and voltage. However, the Fe3+ yield per pulse decreased with increased frequency. To obtain a better understanding of the processes and species involved in the chemical reactions due to plasma exposure, Fe3+ yields were calculated and compared to the experimental data. At higher frequencies, there was insufficient time to complete all the reactions before the next pulse reached the solution; at lower frequencies, the Fe3+ yield was higher because of the relatively longer time available for reactions to occur. In addition, the comparison between DNA damage levels and Fe3+ yields was investigated under different experimental conditions in order to verify the usefulness of both the Fricke solution and the DNA molecule as a probe to characterize APPJs.

Dissociative electron attachment induced ring opening in five-membered heterocyclic compounds.

Five-membered heterocyclic structures, which exist widely in biological systems and play an active role in various biochemical processes, have been studied extensively from a fundamental perspective. Here, the fragmentation patterns of isoxazole, a representative five-membered heterocycle, upon dissociative electron attachment (DEA) were examined carefully by comparing isoxazole's products with those of its methylated derivatives. It was found that the most dominant DEA pathway occurs through the loss of hydrogen at C(3), which leads to ring opening by O-N bond cleavage at an energy of ∼1.5 eV. The ring opening was investigated further for DEA to other related five-membered ring compounds, i.e., oxazole and thiazole. The DEA-induced hydrogen loss was much less pronounced or quenched completely in these two compounds and simultaneous ring-opening behavior was not detected. This observation is of special interest to applied fields, for example, the pharmaceutical industry, because several drugs that contain isoxazole substructures exhibit extensive ring opening during biotransformation.

Electronic Properties of Free-Standing Surfactant-Capped Lead Halide Perovskite Nanocrystals Isolated in Vacuo.

We report an investigation of lead halide perovskite CH3NH3PbBr3 nanocrystals and associated ligand molecules by combining several different state-of-the-art experimental techniques, including synchrotron radiation-based XPS and VUV PES of free-standing nanocrystals isolated in vacuum. By using this novel approach for perovskite materials, we could directly obtain complete band alignment to vacuum of both CH3NH3PbBr3 nanocrystals and the ligands widely used in their preparation. We discuss the possible influence of the ligand molecules to apparent perovskite properties, and we compare the electronic properties of nanocrystals to those of bulk material. The experimental results were supported by DFT calculations.

In situ identification of cation-exchange-induced reversible transformations of 3D and 2D perovskites.

The optical and structural properties of hybrid perovskites can be tuned by the post-synthetic introduction of new cations. To advance the development of this approach, knowledge of the reaction mechanism is essential, but has not yet been elucidated. Here, the effect of n-octylamine on three-dimensional (3D) methylammonium lead bromide (MAPbBr3) was investigated by in situ X-ray photoelectron spectroscopy. Spectroscopic analysis indicated equimolar substitutions between octylammonium (OcA+) and methylammonium (MA+) cations that cause the formation of two-dimensional (2D) octylammonium lead bromide ((OcA)2PbBr4). The introduction of methylamine reversed these changes, and the cation exchange between MA+ and OcA+ caused the reverse conversion to MAPbBr3.

Integrating Ab Initio Simulations and X-ray Photoelectron Spectroscopy: Toward A Realistic Description of Oxidized Solid/Liquid Interfaces.

Many energy storage and conversion devices rely on processes that take place at complex interfaces, where structural and chemical properties are often difficult to probe under operating conditions. A primary example is solar water splitting using high-performance photoelectrochemical cells, where surface chemistry, including native oxide formation, affects hydrogen generation. In this Perspective, we discuss some of the challenges associated with interrogating interface chemistry, and how they may be overcome by integrating high-level first-principles calculations of explicit interfaces with ambient pressure X-ray photoelectron spectroscopy and direct spectroscopic simulations. We illustrate the benefit of this combined approach toward insights into native oxide chemistry at prototypical InP/water and GaP/water interfaces. This example suggests a more general roadmap for obtaining a realistic and reliable description of the chemistry of complex interfaces by combining state-of-the-art computational and experimental techniques.

Low-energy electron-induced dissociation in gas-phase nicotine, pyridine, and methyl-pyrrolidine.

Dissociative electron attachment to nicotine, pyridine, and N-methyl-pyrrolidine was studied in the gas phase in order to assess their stability with respect to low-energy electron interactions. Anion yield curves for different products at electron energies ranging from zero to 15 eV were measured, and the molecular fragmentation pathways were proposed. Nicotine does not form a stable parent anion or a dehydrogenated anion, contrary to other biological systems. However, we have observed complex dissociation pathways involving fragmentation at the pyrrolidine side accompanied by isomerization mechanisms. Combining structure optimization and enthalpy calculations, performed with the Gaussian09 package, with the comparison with a deuterium-labeled N-methyl-d3-pyrrolidine allowed for the determination of the fragmentation pathways. In contrast to nicotine and N-methylpyrrolidine, the dominant pathway in dissociative electron attachment to pyridine is the loss of hydrogen, leading to the formation of an [M-H]- anion. The presented results provide important new information about the stability of nicotine and its constituent parts and contribute to a better understanding of the fragmentation mechanisms and their effects on the biological environment.

Characterization of Neutral Radicals from a Dissociative Electron Attachment Process.

Despite decades of gas-phase studies on dissociative electron attachment (DEA) to various molecules, as yet there has been no direct detection and characterization of the neutral radical species produced by this process. In this study, we performed stepwise electron spectroscopy to directly measure and characterize the neutrals produced upon zero-electron-energy DEA to the model molecule, carbon tetrachloride (CCl_{4}). We observed the direct yield of the trichloromethyl radical (CCl_{3}^{·}) formed by DEA to CCl_{4} and measured the appearance energies of all the other neutral species. By combining these experimental findings with high-level quantum chemical calculations, we performed a complete analysis of both the DEA to CCl_{4} and the subsequent electron-impact ionization of CCl_{3}^{·}. This work paves the way toward a complete experimental characterization of DEA processes, which will lead to a better understanding of the low-energy electron-induced formation of radical species.