Influence of Short-Pulse Microwave Radiation on Thermochemical Properties Aluminum Micropowder.

The thermochemical properties of Al micropowder after exposure to microwave irradiation were investigated. The Al micropowder was exposed to microwave irradiation in air with a frequency of 2.85 GHz, a power density of 8 W/cm2, and a pulse duration of 25 ns and 3 µs. The thermochemical parameters of the irradiated metal powders were determined by the method of thermal analysis at the heating in air. It was found that an increase in the duration of microwave pulses and irradiation time leads to the thermal annealing of the metal particles, and the thermal processes of melting and sintering begin to dominate over non-thermal processes. The specific thermal effect of irradiated Al micropowder oxidation increases from 7744 J/g to 10,154 J/g in comparison with the unirradiated powder. The modeling of thermal heating processes of aluminum (Al) micropowder under the action of pulsed microwave radiation has been performed. It is shown that with an increase in the duration of microwave pulses and irradiation time, a significant heating of the Al micropowder occurs, leading to its melting and sintering. The results of modeling on the action of microwave radiation on the Al micropowder were compared with experimental results.

Compositional Variation in FAPb1-xSnxI3 and Its Impact on the Electronic Structure: A Combined Density Functional Theory and Experimental Study.

Given their comparatively narrow band gap, mixed Pb-Sn iodide perovskites are interesting candidates for bottom cells in all-perovskite tandems or single junction solar cells, and their luminescence around 900 nm offers great potential for near-infrared optoelectronics. Here, we investigate mixed FAPb1-xSnxI3 offering the first accurate determination of the crystal structure over a temperature range from 293 to 100 K. We demonstrate that all compositions exhibit a cubic structure at room temperature and undergo at least two transitions to lower symmetry tetragonal phases upon cooling. Using density functional theory (DFT) calculations based on these structures, we subsequently reveal that the main impact on the band gap bowing is the different energy of the s and p orbital levels derived from Pb and Sn. In addition, this energy mismatch results in strongly composition-dependent luminescence characteristics. Whereas neat and Sn-rich compounds exhibit bright and narrow emission with a clean band gap, Sn-poor compounds intrinsically suffer from increased carrier recombination mediated by in-gap states, as evidenced by the appearance of pronounced low-energy photoluminescence upon cooling. This study is the first to link experimentally determined structures of FAPb1-xSnxI3 with the electronic properties, and we demonstrate that optoelectronic applications based on Pb-Sn iodide compounds should employ Sn-rich compositions.

Nanoscale-Resolved Surface-to-Bulk Electron Transport in CsPbBr3 Perovskite.

Describing the nanoscale charge carrier transport at surfaces and interfaces is fundamental for designing high-performance optoelectronic devices. To achieve this, we employ time- and angle-resolved photoelectron spectroscopy with ultraviolet pump and extreme ultraviolet probe pulses. The resulting high surface sensitivity reveals an ultrafast carrier population decay associated with surface-to-bulk transport, which was tracked with a sub-nanometer spatial resolution normal to the surface, and on a femtosecond time scale, in the case of the inorganic CsPbBr3 lead halide perovskite. The decay time exhibits a pronounced carrier density dependence, which is attributed via modeling to enhanced diffusive transport and concurrent recombination. The transport is found to approach an ordinary diffusive regime, limited by electron-hole scattering, at the highest excitation fluences. This approach constitutes an important milestone in our capability to probe hot-carrier transport at solid interfaces with sub-nanometer resolution in a theoretically and experimentally challenging, yet technologically relevant, high-carrier-density regime.

Lead-Dominated Hyperfine Interaction Impacting the Carrier Spin Dynamics in Halide Perovskites.

The outstanding optical quality of lead halide perovskites inspires studies of their potential for the optical control of carrier spins as pursued in other materials. Entering largely uncharted territory, time-resolved pump-probe Kerr rotation is used to explore the coherent spin dynamics of electrons and holes in bulk formamidinium caesium lead iodine bromide (FA0.9 Cs0.1 PbI2.8 Br0.2 ) and to determine key parameters characterizing interactions of their spins, such as the g-factors and relaxation times. The demonstrated long spin dynamics and narrow g-factor distribution prove the perovskites as promising competitors for conventional semiconductors in spintronics. The dynamic nuclear polarization via spin-oriented holes is realized and the identification of the lead (207 Pb) isotope in optically detected nuclear magnetic resonance proves that the hole-nuclei interaction is dominated by the lead ions. A detailed theoretical analysis accounting for the specifics of the lead halide perovskite materials allows the evaluation of the underlying hyperfine interaction constants, both for electrons and holes. Recombination and spin dynamics evidence that at low temperatures, photogenerated electrons and holes are localized at different regions of the perovskite crystal, resulting in their long lifetimes up to 44 µs. The findings form the base for the tailored development of spin-optoelectronic applications for the large family of lead halide perovskites and their nanostructures.

Nano-Enabled Products: Challenges and Opportunities for Sustainable Agriculture.

Nanotechnology has gained popularity in recent years owing to its established potential for application and implementation in various sectors such as medical drugs, medicine, catalysis, energy, material, and plant science. Nanoparticles (NPs) are smaller in size (1-100 nm) with a larger surface area and have many fruitful applications. The extraordinary functions of NPs are utilized in sustainable agriculture due to nano-enabled products, e.g., nano-insecticides, nano-pesticides, and nano-fertilizers. Nanoparticles have lately been suggested as an alternate method for controlling plant pests such as insects, fungi, and weeds. Several NPs exhibit antimicrobial properties considered in food packaging processes; for example, Ag-NPs are commonly used for such purposes. Apart from their antimicrobial properties, NPs such as Si, Ag, Fe, Cu, Al, Zn, ZnO, TiO2, CeO2, Al2O3, and carbon nanotubes have also been demonstrated to have negative impacts on plant growth and development. This review examines the field-use of nano-enabled products in sustainable agriculture, future perspectives, and growing environmental concerns. The remarkable information on commercialized nano-enabled products used in the agriculture and allied sectors are also provided.

Thermal Stability and Flammability of Epoxy Composites Filled with Multi-Walled Carbon Nanotubes, Boric Acid, and Sodium Bicarbonate.

Epoxy composites filled with 0.5 wt% of multi-walled carbon nanotubes (MWCNTs), 10 and 15 wt% of boric acid and sodium bicarbonate separately, as well as composites filled with a combination of MWCNTs-boric acid and MWCNTs-sodium bicarbonate were prepared. The thermal behavior of the prepared samples was investigated under heating in oxidative environment using thermogravimetric analysis. The hardness was measured using the Shore D hardness test. To evaluate the flammability of the samples, the ignition temperature and time-to-ignition were determined. It was concluded that sodium bicarbonate in the studied concentrations (10 and 15 wt%) is not appropriate for use as a filler capable of improving the thermooxidative stability and reducing the flammability of epoxy polymers. The improvement in the thermal properties can be achieved by using the combination of boric acid and multi-walled carbon nanotubes as fillers. The thermooxidative destruction of the samples filled with boric acid passes more slowly and more evenly via the formation of B2O3 as a result of its decomposition.

Environmental and human health risk assessment of potentially toxic elements in soils around the largest coal-fired power station in Southern Russia.

The combustion of solid fuel at power plants pollutes adjacent areas with potentially toxic elements (PTEs), which increases risks to public health in the vicinity of these facilities. The proposed paper presents the results of a geochemical study of PTEs (Cr, Mn, Ni, Cu, Zn, Cd, and Pb) contamination in the vicinity of Novocherkassk Power Plant (NPP) as it relates to environmental and human health risks. The impact zone of NPP is pronounced for a distance of approximately 7 km northwest of the enterprise-the second largest coal power plant in Southern Russia. Data from monitoring sites lead us to conclude that spatial patterns of soil pollution are strongly influenced by the peculiarities of local atmospheric circulation, while the characteristics of soils within the study area play a secondary role. The highest levels of PTEs and their exchangeable forms exceed both regional background and sanitary and hygienic standards within a radius of 3 km to the west of the plant, which corresponds to a zone of soils contaminated with Cr, Ni, Cu, Zn, Cd, and Pb. The carcinogenic risk to human health slightly exceeds the permissible standard of 1 × 10-6 for soils in close vicinity of the enterprise due to the potential human intake of Ni, Cd, and Pb. The results of the health risk assessment indicate no noncarcinogenic risks for adults, while for children, they are low.

Comparison of Heavy Metal Content in Artemisia austriaca in Various Impact Zones.

A study on Artemisia austriaca of two anthropogenically heavy metal-polluted impact zones of the Rostov region, namely Lake Atamanskoye and Novocherkasskaya Power Station, was conducted. The influence of soil pollution on the Pb, Zn, and Cu accumulation in various organs of A. austriaca, which is widespread in the studied territories, was established. An extremely high level of Zn content (3051 mg/kg) was observed in the soils of the impact zone of Lake Atamanskoe, as well as an excess over the maximum permissible level for Pb and Cu (32 and 132 mg/kg accordingly). The distribution coefficient (DC) of heavy metal translocation showed the highest mobility of Zn (DC ≥ 1 in 9 out of 11 sites) and the smallest of Pb (DC ≥ 1 in 4 out of 11 sites) in plants of the Novocherkasskaya Power Station impact zone. The zone of increased pollution around Lake Atamanskoye was 1.5 km, which was much smaller than the Novocherkasskaya Power Station zone of high pollution (5 km). However, vehicle emissions accumulated in the soil over the past decades had a greater effect on the Pb translocation than atmospheric emissions of the enterprise.

Lead-Halide Scalar Couplings in 207Pb NMR of APbX3 Perovskites (A = Cs, Methylammonium, Formamidinium; X = Cl, Br, I).

Understanding the structure and dynamics of newcomer optoelectronic materials - lead halide perovskites APbX3 [A = Cs, methylammonium (CH3NH3+, MA), formamidinium (CH(NH2)2+, FA); X = Cl, Br, I] - has been a major research thrust. In this work, new insights could be gained by using 207Pb solid-state nuclear magnetic resonance (NMR) spectroscopy at variable temperatures between 100 and 300 K. The existence of scalar couplings 1JPb-Cl of ca. 400 Hz and 1JPb-Br of ca. 2.3 kHz could be confirmed for MAPbX3 and CsPbX3. Diverse and fast structure dynamics, including rotations of A-cations, harmonic and anharmonic vibrations of the lead-halide framework and ionic mobility, affect the resolution of the coupling pattern. 207Pb NMR can therefore be used to detect the structural disorder and phase transitions. Furthermore, by comparing bulk and nanocrystalline CsPbBr3 a greater structural disorder of the PbBr6-octahedra had been confirmed in a nanoscale counterpart, not readily captured by diffraction-based techniques.

Vibrational dynamics in lead halide hybrid perovskites investigated by Raman spectroscopy.

Lead halide perovskite semiconductors providing record efficiencies of solar cells have usually mixed compositions doped in A- and X-sites to enhance the phase stability. The cubic form of formamidinium (FA) lead iodide reveals excellent opto-electronic properties but transforms at room temperature (RT) into a hexagonal structure which does not effectively absorb visible light. This metastable form and the mechanism of its stabilization by Cs+ and Br- incorporation are poorly characterized and insufficiently understood. We report here the vibrational properties of cubic FAPbI3 investigated by DFT calculations on phonon frequencies and intensities, and micro-Raman spectroscopy. The effects of Cs+ and Br- partial substitution are discussed. We support our results with the study of FAPbBr3 which expands the identification of vibrational modes to the previously unpublished low frequency region (<500 cm-1). Our results show that the incorporation of Cs+ and Br- leads to the coupling of the displacement of the A-site components and weakens the bonds between FA+ and the PbX6 octahedra. We suggest that the enhancement of α-FAPbI3 stability can be a product of the release of tensile stresses in the Pb-X bond, which is reflected in a red-shift of the low frequency region of the Raman spectrum (<200 cm-1).

Accumulation and transformation of benzo[a]pyrene in Haplic Chernozem under artificial contamination.

Polycyclic aromatic hydrocarbons (PAHs) have been a major concern because of their carcinogenicity, mutagenicity, teratogenicity and wide distribution in the environment. Over 90% of PAHs in the environment exist on soil surface/sediment. Benzo[a]pyrene (BaP) is one of the predominant PAHs in soil. Thus, it is critically important to understand the patterns of BaP accumulation and transformation peculiarities in soil for the risk assessment. The studies were conducted in model experiment with Haplic Chernozem spiked with various doses of BaP (20, 200, 400 and 800 µg kg-1) equivalent to 1, 10, 20 and 40 levels of maximum permissible concentrations. The unique properties of Haplic Chernozem were studied allow to accumulate and transform BaP as well as barley plants ability to absorb of some BaP concentration. Extraction of BaP from the soil was carried out by the saponification method. The qualitative and quantitative determination of BaP and other polycyclic aromatic hydrocarbons (PAHs) was performed by high-performance liquid chromatography with fluorescence detection (Agilent 1260 Germany, 2014). BaP accumulation in soil depended on the applied BaP concentrations in Haplic Chernozem. Studying the features of PAHs transformation in the soil of a model experiment 1 year after the compound application showed the BaP content in the soil decreased up to 11-40%. Two years after the BaP application the content in the soil decreased up to 15-44% from the initial BaP content in the soil. The percentage of BaP concentration reduction in Haplic Chernozem increased with an increase in the dose of the applied xenobiotic. An increase in the dose of the applied pollutant to the soil of the model experiment contributed to an increase in all PAHs, which indicated a rapid BaP transformation in Haplic Chernozem. The PAHs content in the soils of model experiment in the first year of the research formed the following descending series: pyrene > chrysene > fluoranthene > phenanthrene. In the second year of research the phenanthrene content became higher than the fluoranthene content. The content of these compounds exceeded 20% of the total PAHs content in the soil samples in the first and second years of the model experiment. The features of PAHs accumulation and transformation in soils under artificial pollution showed the degradation of large-nuclear PAHs, starting from 5-ring polyarenes, and their structural reorganization into the less-nuclear polyarenes, such as 4-, 3-, and 2-ring PAHs. During the 2 years of the model experiment the BaP concentration in the soil decreased up to 15-44% from the initial BaP content in the soil.

High-resolution remote thermometry and thermography using luminescent low-dimensional tin-halide perovskites.

Although metal-halide perovskites have recently revolutionized research in optoelectronics through a unique combination of performance and synthetic simplicity, their low-dimensional counterparts can further expand the field with hitherto unknown and practically useful optical functionalities. In this context, we present the strong temperature dependence of the photoluminescence lifetime of low-dimensional, perovskite-like tin-halides and apply this property to thermal imaging. The photoluminescence lifetimes are governed by the heat-assisted de-trapping of self-trapped excitons, and their values can be varied over several orders of magnitude by adjusting the temperature (up to 20 ns °C-1). Typically, this sensitive range spans up to 100 °C, and it is both compound-specific and shown to be compositionally and structurally tunable from -100 to 110 °C going from [C(NH2)3]2SnBr4 to Cs4SnBr6 and (C4N2H14I)4SnI6. Finally, through the implementation of cost-effective hardware for fluorescence lifetime imaging, based on time-of-flight technology, these thermoluminophores have been used to record thermographic videos with high spatial and thermal resolution.

Tuning Transport Properties in Thermoelectric Nanocomposites through Inorganic Ligands and Heterostructured Building Blocks.

Methodologies that involve the use of nanoparticles as "artificial atoms" to rationally build materials in a bottom-up fashion are particularly well-suited to control the matter at the nanoscale. Colloidal synthetic routes allow for an exquisite control over such "artificial atoms" in terms of size, shape, and crystal phase as well as core and surface compositions. We present here a bottom-up approach to produce Pb-Ag-K-S-Te nanocomposites, which is a highly promising system for thermoelectric energy conversion. First, we developed a high-yield and scalable colloidal synthesis route to uniform lead sulfide (PbS) nanorods, whose tips are made of silver sulfide (Ag2S). We then took advantage of the large surface-to-volume ratio to introduce a p-type dopant (K) by replacing native organic ligands with K2Te. Upon thermal consolidation, K2Te-surface modified PbS-Ag2S nanorods yield p-type doped nanocomposites with PbTe and PbS as major phases and Ag2S and Ag2Te as embedded nanoinclusions. Thermoelectric characterization of such consolidated nanosolids showed a high thermoelectric figure-of-merit of 1 at 620 K.

Guanidinium and Mixed Cesium-Guanidinium Tin(II) Bromides: Effects of Quantum Confinement and Out-of-Plane Octahedral Tilting.

Hybrid organic-inorganic main-group metal halide compounds are the subject of intense research owing to their unique optoelectronic characteristics. In this work, we report the synthesis, structure, and electronic and optical properties of a family of hybrid tin (II) bromide compounds comprising guanidinium [G, C(NH2)3 +] and mixed cesium-guanidinium cations: G2SnBr4, CsGSnBr4, and Cs2GSn2Br7. G2SnBr4 has a one-dimensional structure that consists of chains of corner-sharing [SnBr5]2- square pyramids and G cations situated in between the chains. Cs+ exhibits a pronounced structure-directing effect where a mixture of Cs+ and G cations forms mono- and bilayered two-dimensional perovskites: CsGSnBr4 and Cs2GSn2Br7. Furthermore, the flat shapes of the guanidinium cations induce anisotropic out-of-plane tilts of the [SnBr6]4- octahedra in the CsGSnBr4 and Cs2GSn2Br7 compounds. In G2SnBr4, the Sn lone pair is highly stereoactive and favors non-octahedral, that is, square pyramidal coordination of Sn(II). G2SnBr4 exhibits bright broad-band emission from self-trapped excitonic states, owing to its soft lattice and electronic localization. This emission in G2SnBr4 is characterized by a photoluminescence (PL) quantum yield of 2% at room temperature (RT; 75 ± 5% at 77 K) and a fast PL lifetime of 18 ns at room temperature.

Environmental pollution of soil with PAHs in energy producing plants zone.

Polycyclic aromatic hydrocarbons (PAHs) are widely distributed environmental toxicants primarily formed during the incomplete combustion of organic materials (for example, coal, oil, gasoline and wood). Power energy plants are the main sources of organic contaminants including PAHs. The purpose of the present research was to study the Novocherkassk Electric Power Station (NEPS) emission effects of PAHs accumulation in soils. The regional levels, types (groups) and spatial distribution of 16 priority PAHs were investigated. The monitoring sites were located on fallow lands of the 20 km around NEPS. PAHs extraction from collected soil samples was performed using the ecologically clean express-method of subcritical water extraction. The total PAHs content gradually increased in soil of the studied territories during 2016-2017 due to an increase in contaminants emission. Accordingly 16 priority PAHs were determined in the soil samples collected from the sites located to the northwest from NEPS in direction of predominant winds. The 5-km zone situated in direction of predominant winds was highly subjected to PAHs contamination, with maximal accumulation at a distance of 1.6 km from the source. The ratio of high- and low-molecular weight PAHs content in soils of monitoring sites was taken as an index of environmental soil contamination. The high-molecular weight PAHs concentration prevailed in monitoring sites soils situated in direction of predominant winds from NEPS, while the concentration of low-molecular weight PAHs prevailed in the monitoring sites soils situated around NEPS. Soil properties also influenced PAHs accumulation. Polyarenes content in Haplic Chernozems and Haplic Chernozems (Stagnic) was higher versus Fluvisols. This study provides the understanding and model the fate of PAHs in regional technogenic landscape.

Highly Emissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional Tin Halides.

The spatial localization of charge carriers to promote the formation of bound excitons and concomitantly enhance radiative recombination has long been a goal for luminescent semiconductors. Zero-dimensional materials structurally impose carrier localization and result in the formation of localized Frenkel excitons. Now the fully inorganic, perovskite-derived zero-dimensional SnII material Cs4 SnBr6 is presented that exhibits room-temperature broad-band photoluminescence centered at 540 nm with a quantum yield (QY) of 15±5 %. A series of analogous compositions following the general formula Cs4-x Ax Sn(Br1-y Iy )6 (A=Rb, K; x≤1, y≤1) can be prepared. The emission of these materials ranges from 500 nm to 620 nm with the possibility to compositionally tune the Stokes shift and the self-trapped exciton emission bands.

Low-Cost Synthesis of Highly Luminescent Colloidal Lead Halide Perovskite Nanocrystals by Wet Ball Milling.

Lead halide perovskites of APbX3 type [A = Cs, formamidinium (FA), methylammonium; X = Br, I] in the form of ligand-capped colloidal nanocrystals (NCs) are widely studied as versatile photonic sources. FAPbBr3 and CsPbBr3 NCs have become promising as spectrally narrow green primary emitters in backlighting of liquid-crystal displays (peak at 520-530 nm, full width at half-maximum of 22-30 nm). Herein, we report that wet ball milling of bulk APbBr3 (A = Cs, FA) mixed with solvents and capping ligands yields green luminescent colloidal NCs with a high overall reaction yield and optoelectronic quality on par with that of NCs of the same composition obtained by hot-injection method. We emphasize the superiority of oleylammonium bromide as a capping ligand used for this procedure over the standard oleic acid and oleylamine. We also show a mechanically induced anion-exchange reaction for the formation of orange-emissive CsPb(Br/I)3 NCs.

Optogenetic regulation of transcription.

Optogenetics has become widely recognized for its success in real-time control of brain neurons by utilizing non-mammalian photosensitive proteins to open or close membrane channels. Here we review a less well known type of optogenetic constructs that employs photosensitive proteins to transduce the signal to regulate gene transcription, and its possible use in medicine. One of the problems with existing gene therapies is that they could remain active indefinitely while not allowing regulated transgene production on demand. Optogenetic regulation of transcription (ORT) could potentially be used to regulate the production of a biological drug in situ, by repeatedly applying light to the tissue, and inducing expression of therapeutic transgenes when needed. Red and near infrared wavelengths, which are capable of penetration into tissues, have potential for therapeutic applications. Existing ORT systems are reviewed herein with these considerations in mind.

The role of Alu-derived RNAs in Alzheimer's and other neurodegenerative conditions.

Non-coding RNAs have emerged as essential contributors to neuroinflammation. The Alu element is the most abundant potential source of non-coding RNA in the human genome represented by over 1.1 million copies totaling ∼10% of the genome's mass. Accumulation of "Alu RNA" was observed in the brains of individuals with dementia and Creutzfeldt-Jakob disease - a degenerative brain disorder. "Alu RNAs" activate inflammatory pathways and apoptosis in the non-neural cells. In particular, the "Alu RNA" cytotoxicity is suggested as a mechanism in retinal pigment epithelium (RPE), a compartment damaged in the process of age-related macular degeneration. In RPE cells, the deficiency of Dicer is reported to lead to an accumulation of P3Alu transcripts, subsequent activation of the ERK1/2 signaling pathway, and the formation of NLRP3 inflammasome. In turn, these events result in RPE cell death by apoptosis. Importantly, RPE cells are of neuroectodermal origin, these cells display more similarity to neurons than to other epithelial cells. Thus, it is plausible that the mechanisms of "Alu RNA" cytotoxicity in brain neurons are similar to that in RPE. We hypothesize that accumulation of polymerase III-transcribed noncoding RNA of Alu (P3Alu) may contribute to both neuroinflammation and neurodegeneration associated with Alzheimer's disease (AD) and other degenerative brain disorders. This hypothesis points toward a novel molecular pathway not previously considered for the treatment of AD.

Colloidal CsPbX3 (X = Cl, Br, I) Nanocrystals 2.0: Zwitterionic Capping Ligands for Improved Durability and Stability.

Colloidal lead halide perovskite nanocrystals (NCs) have recently emerged as versatile photonic sources. Their processing and optoelectronic applications are hampered by the loss of colloidal stability and structural integrity due to the facile desorption of surface capping molecules during isolation and purification. To address this issue, herein, we propose a new ligand capping strategy utilizing common and inexpensive long-chain zwitterionic molecules such as 3-(N,N-dimethyloctadecylammonio)propanesulfonate, resulting in much improved chemical durability. In particular, this class of ligands allows for the isolation of clean NCs with high photoluminescence quantum yields (PL QYs) of above 90% after four rounds of precipitation/redispersion along with much higher overall reaction yields of uniform and colloidal dispersible NCs. Densely packed films of these NCs exhibit high PL QY values and effective charge transport. Consequently, they exhibit photoconductivity and low thresholds for amplified spontaneous emission of 2 µJ cm-2 under femtosecond optical excitation and are suited for efficient light-emitting diodes.