Effects of Pulsed Electric Field on the Physicochemical and Structural Properties of Micellar Casein.

Pulsed electric field (PEF) as a green processing technology is drawing greater attention due to its eco-friendliness and potential to promote sustainable development goals. In this study, the effects of different electric field strengths (EFS, 0-30 kV/cm) on the structure and physicochemical features of casein micelles (CSMs) were investigated. It was found that the particle sizes of CSMs increased at low EFS (10 kV/cm) but decreased at high EFS (30 kV/cm). The absolute ζ-potential at 30 kV/cm increased from -26.6 (native CSMs) to -29.5 mV. Moreover, it was noticed that PEF treatment leads to changes in the surface hydrophobicity; it slightly increased at low EFS (10 kV/cm) but decreased at EFS > 10 kV/cm. PEF enhanced the protein solubility from 84.9 (native CSMs) to 87.1% (at 10 kV/cm). PEF at low EFS (10 kV/cm) intensified the emission fluorescence spectrum of CSMs, while higher EFS reduced the fluorescence intensity compared to native CSMs. Moreover, the analysis of the Amide Ι region showed that PEF-treated CSMs reduced the α-helix and increased the ß-sheet content. Raman spectra confirmed that PEF treatment > 10 kV/cm buried tyrosine (Tyr) residues in a hydrophobic environment. It was also found that PEF treatment mainly induced changes in the disulfide linkages. In conclusion, PEF technology can be employed as an eco-friendly technology to change the structure and physiochemical properties of CSMs; this could improve their techno-functional properties.

Antimicrobial particles based on Cu2ZnSnS4 monograins.

In this research, Cu2ZnSnS4 (CZTS) particles were successfully fabricated via the molten salt approach from the copper, zinc and tin sulphides as raw precursors. SEM analysis revealed that CZTS particles are tetragonal-shaped with sharp edges, smooth flat plane morphology, and crystal size varying from 10.8 to 28.7 µm. The phase and crystalline structure of synthesized powders were investigated using XRD analysis, which confirms the presence of a tetragonal crystal structure kesterite phase. The chemical composition of CZTS particles was evaluated by EDX spectroscopy, which identified the nearly stoichiometric composition with an averaged formula of Cu1.88Zn1.04SnS3.97. The TG/DTA-MS and ICP-OES analysis showed the possible decomposition pathways and predicted their degradation rate in aqueous solutions. The CZTS particles possessed highly effective concentration and time-dependent antimicrobial properties against medically relevant bacteria and yeast strains. The CZTS particles (1 g L-1) exhibited over 95.7 ± 1.9% killing efficiency towards M. luteus. In contrast, higher dosages (3.5 and 5 g L-1) led to its complete inactivation and reduced the P. aeruginosa cell viability to 43.2 ± 3.2% and 4.1 ± 1.1%, respectively. Moreover, the CZTS particles (0.5 g L-1) are responsible for causing 54.8 ± 1.8% of C. krusei and 89.7 ± 2.1% of C. parapsilosis yeasts death within the 24 h of exposure, which expanded to almost 100% when yeasts were treated with two times higher CZTS concentration (1.0 g L-1). The mechanism of action has been proposed and evidenced by monitoring the 2',7'-dichlorofluorescein (DCF) fluorescence, which revealed that the overproduction of reactive oxygen species (ROS) is responsible for microorganism death.

Seed Layer Optimisation for Ultra-Thin Sb2Se3 Solar Cells on TiO2 by Vapour Transport Deposition.

Antimony selenide (Sb2Se3) material has drawn considerable attention as an Earth-abundant and non-toxic photovoltaic absorber. The power conversion efficiency of Sb2Se3-based solar cells increased from less than 2% to over 10% in a decade. Different deposition methods were implemented to synthesize Sb2Se3 thin films, and various device structures were tested. In search of a more environmentally friendly device composition, the common CdS buffer layer is being replaced with oxides. It was identified that on oxide substrates such as TiO2 using vacuum-based close-space deposition methods, an intermediate deposition step was required to produce high-quality thin films. However, little or no investigation was carried out using another very successful vacuum deposition approach in Sb2Se3 technology called vapour transport deposition (VTD). In this work, we present optimized VTD process conditions to achieve compact, pinhole-free, ultra-thin (<400 nm) Sb2Se3 absorber layers. Three process steps were designed to first deposit the seed layer, then anneal it and, at the final stage, deposit a complete Sb2Se3 absorber. Fabricated solar cells using absorbers as thin as 400 nm generated a short-circuit current density over 30 mA/cm2, which demonstrates both the very high absorption capabilities of Sb2Se3 material and the prospects for ultra-thin solar cell application.

Preparation of Graphene Oxide-Maghemite-Chitosan Composites for the Adsorption of Europium Ions from Aqueous Solutions.

The adsorption of Eu(III) on composites synthesised from graphene oxide (GO), maghemite (MGH), and chitosan (CS) has been studied using different approaches. The physicochemical and morphological characteristics of the composites GO-MGH, GO-CS, GO-MGH-CS I, II, and III were determined by XRD, Mössbauer spectroscopy, FTIR, Raman spectroscopy, and TEM. According to the results of batch experiments, the maximum experimental adsorption capacity was 52, 54, 25, 103, and 102 mg/g for GO-MGH, GO-CS, GO-MGH-CS I, II, and III, respectively. The data obtained are in better agreement with the Langmuir, pseudo-second-order, and pseudo-first-order models only for GO-MGH. Thus, the adsorption of Eu(III) on the composites was a favourable, monolayer, and occurred at homogeneous sites. The nature of adsorption is chemical and, in the case of GO-MGH, physical. Tests of the composites in natural waters showed a high removal efficiency for Eu(III), Pu(IV), and Am(III), ranging from 74 to 100%. The ANFIS model has quite good predictive ability, as shown by the values for R2, MSE, SSE, and ARE. The GO-MGH-CS composites with the high adsorption capacity could be promising candidates for the removal of Eu(III) and the pre-concentration of Pu(IV) and Am(III) from natural waters.

Adsorption of caesium and cobalt ions on the muscovite mica clay-graphene oxide-γ-Fe2O3-Fe3O4 composite.

The muscovite mica clay-graphene oxide-maghemite-magnetite (γ-Fe2O3-Fe3O4) composite was first used for the adsorption of caesium(I) and cobalt(II). The presence of clay minerals, graphene oxide, maghemite, and magnetite was detected in the prepared composite by XRD, WD-XRF, Mössbauer spectroscopy, and ATR-FTIR. The SEM and TEM results show that the composite has a layered structure with irregularly shaped pores on the surface. It was found that the adsorption of ions depends on the initial concentration, pH (except for caesium), mass of adsorbent, temperature, and contact time. The maximum adsorption capacity for Cs(I) and Co(II) was 2286 mg/g and 652 mg/g, respectively, and was obtained at concentrations (Cs(I) = 12,630 mg/L; Co(II) = 3200 mg/L), adsorbent mass of 0.01 g, pH (Cs(I) = 7; Co(II) = 5), temperature of 20 ± 1 °C, and contact time of 24 h. The high adsorption capacity of the composite could be due to a diversity of functional groups, a large number of active sites or the multilayer adsorption of caesium and cobalt ions on the surface of the composite. The Freundlich, Langmuir isotherms, and the pseudo-second-order kinetic model better describe the adsorption of these ions on the composite. The adsorption was non-spontaneous endothermic for Cs(I) and spontaneous endothermic for Co(II). The proposed mechanism of adsorption of Cs and Co ions on the composite is complex and involves electrostatic interactions and ion exchange. The ANFIS model proved to be quite effective in predicting the adsorption of Cs(I) and Co(II), as shown by the obtained values of R2, MSE, SSE, and ARE.

The impact of co-treatment with graphene oxide and metal mixture on Salmo trutta at early development stages: The sorption capacity and potential toxicity.

Graphene oxide (GO) are novel nanomaterials with a wide range of applications due to their high absorption capacity. This study was undertaken with a view to assess the bioaccumulation and acute toxicity of GO used in combination with the heavy metal mixture (Cr, Cu, Ni and Zn) to fish embryos and larvae. For this purpose, Salmo trutta embryos and larvae were subjected to the 4-day long treatment with three different concentrations of GO, the metal mixture, which was prepared of four metals at the concentrations corresponding to the maximum-permissible-concentrations for EU inland waters (Cr-0.01, Cu-0.01, Ni-0.034, and Zn-0.1 mg/L), and with GO in combination with MIX (GO+MIX). When used in combination with the metal mixture, GO exhibited a high metal sorption capacity. The obtained confocal fluorescence microscopy results showed that GO located in the embryo chorion causing its damage; in larvae, however, GO were found only in the gill region. Results of these experiments confirmed the hypothesis that GO affects the accumulation of metals and mitigates their toxic effects on organism. In embryos, the acute toxicity of exposure to GO and co-exposure to MIX+GO was found to manifest itself through the decreased heart rate (HR) and malondialdehyde (MDA) level and through the increased metallothionein (MT) concentration. Meanwhile, in larvae, GO and MIX+GO were found to induce genotoxicity effects. However, changes in HR, MDA, MT, gill ventilation frequency, yolk sack absorption and cytotoxicity compared with those of the control group were not recorded in larvae. The obtained results confirmed our hypothesis: the combined effect of MIX and GO was less toxic to larvae (especially survival) than individual effects of MIX components. However, our results emphasize that fish exposure to GO alone and in combination with heavy metal contaminants (MIX+GO) even at environmentally relevant concentrations causes health risks that cannot be ignored.

Synthesis and physical characteristics of narrow bandgap chalcogenide SnZrSe 3.

Background: The development of organic/inorganic metal halide perovskites has seen unprecedent growth since their first recognition for applications in optoelectronic devices. However, their thermodynamic stability and toxicity remains a challenge considering wide-scale deployment in the future. This spurred an interest in search of perovskite-inspired materials which are expected to retain the advantageous material characteristics of halide perovskites, but with high thermodynamic stability and composed of earth-abundant and low toxicity elements. ABX 3 chalcogenides (A, B=metals, X=Se, S) have been identified as potential class of materials meeting the aforementioned criteria. Methods: In this work, we focus on studying tin zirconium selenide (SnZrSe 3) relevant physical properties with an aim to evaluate its prospects for application in optoelectronics. SnZrSe 3 powder and monocrystals were synthesized via solid state reaction in 600 - 800 °C temperature range. Crystalline structure was determined using single crystal and powder X-ray diffraction methods. The bandgap was estimated from diffused reflectance measurements on powder samples and electrical properties of crystals were analysed from temperature dependent I-V measurements. Results: We found that SnZrSe 3 crystals have a needle-like structure (space group - Pnma) with following unit cell parameters: a=9.5862(4) Å, b=3.84427(10) Å, c=14.3959(5) Å. The origin of the low symmetry crystalline structure was associated with stereochemical active electron lone pair of Sn cation. Estimated bandgap was around 1.15 eV which was higher than measured previously and predicted theoretically. Additionally, it was found that resistivity and conductivity type depended on the compound chemical composition. Conclusions: Absorption edge in the infrared region and bipolar dopability makes SnZrSe 3 an interesting material candidate for application in earth-abundant and non-toxic single/multi-junction solar cells or other infrared based optoelectronic devices.

Impact of soil organic matter on Pu migration in five Lithuanian surface soils.

Pu distribution coefficient Kd variation was experimentally determined and examined in natural soil samples considering the type of soil, particle size, pH, the concentration of macroelements and organic matter content. This research was carried out with sand, silty sand, peat, clayey sand and clayey loam samples by applying 236Pu tracer in flow-through column tests. Due to relatively short contact time of 0.5-40 h the tests are considered as have not reached equilibrium state and represent the fast-moving contaminants retardation processes closer to field conditions. Every soil sample was fractionated into two particle size fractions: ≤0.25 mm and 0.25 ÷ 0.5 mm. Analysis revealed that Kd of Pu is higher for the smaller soil particle fraction (≤0.25 mm). The experimental study with 1.6, 4, 6 and 9 pH tracer solution revealed a tendency of elevated Kd when 4 pH and 6 pH solutions were applied, but obtained Kd values were not correlated with initial soil pH due to high buffering capacity of soils. This study shows a very significant influence (r = 0.98) of organic matter content on the Pu distribution coefficient. The Kd of Pu for the fine fraction of peat soil with high organic matter content (67%) reached maximum values of 6597 L/kg and 6200 L/kg when tracer solution was applied of pH = 4 and pH = 6, respectively. In comparison, the minimum Kd value of 3.9 L/kg was obtained for the coarse silty sand fraction with the lowest organic matter content of 1.3% at tracer pH = 1.6. A statistically reliable high correlations of r = 0.95 and 0.94 were also observed between Kd and specific soil elements Mg and Pb content in soils, respectively. The content of Fe in soils was significantly correlated (r = 0.67) with the Kd values of plutonium as well. However, the organic matter content in soils appeared to be the governing factor determining good correlations and causing the highest Kd of Pu values.

Suppression of Electric Field-Induced Segregation in Sky-Blue Perovskite Light-Emitting Electrochemical Cells.

Inexpensive perovskite light-emitting devices fabricated by a simple wet chemical approach have recently demonstrated very prospective characteristics such as narrowband emission, low turn-on bias, high brightness, and high external quantum efficiency of electroluminescence, and have presented a good alternative to well-established technology of epitaxially grown III-V semiconducting alloys. Engineering of highly efficient perovskite light-emitting devices emitting green, red, and near-infrared light has been demonstrated in numerous reports and has faced no major fundamental limitations. On the contrary, the devices emitting blue light, in particular, based on 3D mixed-halide perovskites, suffer from electric field-induced phase separation (segregation). This crystal lattice defect-mediated phenomenon results in an undesirable color change of electroluminescence. Here we report a novel approach towards the suppression of the segregation in single-layer perovskite light-emitting electrochemical cells. Co-crystallization of direct band gap CsPb(Cl,Br)3 and indirect band gap Cs4Pb(Cl,Br)6 phases in the presence of poly(ethylene oxide) during a thin film deposition affords passivation of surface defect states and an increase in the density of photoexcited charge carriers in CsPb(Cl,Br)3 grains. Furthermore, the hexahalide phase prevents the dissociation of the emissive grains in the strong electric field during the device operation. Entirely resistant to 5.7 × 106 V·m-1 electric field-driven segregation light-emitting electrochemical cell exhibits stable emission at wavelength 479 nm with maximum external quantum efficiency 0.7%, maximum brightness 47 cd·m-2, and turn-on bias of 2.5 V.

Electronic structure of CsPbBr3-xClx perovskites: synthesis, experimental characterization, and DFT simulations.

All-inorganic lead halide perovskites of various compositions have emerged as a prospective family of materials for light-emitting devices and photonic applications. However, a comprehensive study of their structural and electronic properties is still missing. Moreover, thin film fabrication of these perovskites comprising heterohalide anions by wet chemistry approaches also remains challenging. Here we fabricate high-quality CsPbBr3-xClx perovskite thin films using a wet chemical method accompanied by a chemical vapor anion exchange procedure, which allows rigorously studying their optical and structural properties at different compositions. Namely, we present both the numerical and experimental studies of the electronic properties of all-inorganic mixed-halide perovskites, showing their optical absorption, excitonic photoluminescence and exciton binding energy, phase, chemical composition, and band structure and the band gap evolution with a gradual change in x in CsPbBr3-xClx. The results reveal that as Cl ions substitute for Br ones in the perovskite crystal lattice the room-temperature phase does not change its orthorhombic symmetry, whereas the energy of the direct electronic transition from the valence to conduction band at the Γ-point increases nonlinearly. By using the experimentally derived nonlinear dependence it is easy to accurately predict the band gap for any CsPbBr3-xClx perovskite thin film consisting of grains with sizes beyond the quantum confinement regime.

MoS2 with Organic Fragment - a New Hybrid Material for Laser Writing.

New nanostructured metasurfaces capable change the composition and physical properties upon pulse laser excitation recently received a marked attention for nanophotonic technologies. In this study, well adherent to the metal substrate and significantly thicker nanoplatelet-shaped MoS2-based arrays were synthesized by one pot hydrothermal way via addition of ethanolamine in the synthesis solution containing ammonium heptamolybdate and thiourea. It was shown that the lightening of this material with green light ns-laser pulses at a suitable fluencies results in the detachment of organic species and compositional transformations to significantly pure MoS2 material. For characterization the synthesized products scanning electron microscopy (SEM), glancing angle X-ray diffraction (GA-XRD), diffuse reflection, Raman, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) methods before and following green light picosecond laser pulse illumination were applied. We envisaged that these films can be successfully used as metamaterial for laser writing.

A Few-Minute Synthesis of CsPbBr3 Nanolasers with a High Quality Factor by Spraying at Ambient Conditions.

Inorganic cesium lead halide perovskite nanowires, generating laser emission in the broad spectral range at room temperature and low threshold, have become powerful tools for the cutting-edge applications in the optoelectronics and nanophotonics. However, to achieve high-quality nanowires with the outstanding optical properties, it was necessary to employ long-lasting and costly methods of their synthesis, as well as postsynthetic separation and transfer procedures that are not convenient for large-scale production. Here we report a novel approach to fabricate high-quality CsPbBr3 nanolasers obtained by rapid precipitation from dimethyl sulfoxide solution sprayed onto hydrophobic substrates at ambient conditions. The synthesis technique allows producing the well-separated nanowires with a broad size distribution of 2-50 µm in 5-7 min, being the fastest method to the best of our knowledge. The formation of nanowires occurs via ligand-assisted reprecipitation triggered by intermolecular proton transfer from (CH3)2CHOH to H2O in the presence of a minor amount of water. The XRD patterns confirm an orthorhombic crystal structure of the as-grown CsPbBr3 single nanowires. Scanning electron microscopy images reveal their regular shape and truncated pyramidal end facets, while high-resolution transmission electron microscopy ones demonstrate their single-crystal structure. The lifetime of excitonic emission of the nanowires is found to be 7 ns, when the samples are excited with energy below the lasing threshold, manifesting the low concentration of defect states. The measured nanolasers of different lengths exhibit pronounced stimulated emission above 13 µJ cm-2 excitation threshold with quality factor Q = 1017-6166. Their high performance is assumed to be related to their monocrystalline structure, low concentration of defect states, and improved end facet reflectivity.