Probing the effect of precursor concentration on the growth and properties of titanium dioxide nanocones for environment safe solar cells.

Environment friendly third-generation solar cells sensitized by dyes, quantum dots, and perovskites are seen as promising energy alternatives. Among the various strategies, employing one-dimensional nanostructures that exemplify the smallest dimension for efficient carrier transport rate from the active layer to electron transport layer (ETL) in photovoltaic devices is attempted in this work. We herein report the synthesis of well-aligned 1-D TiO2 nanocones as ETL for photovoltaic thin films by varying the precursor concentration (0.03 M, 0.04 M, 0.05 M) to track the evolution of growth. The hydrothermal approach is exploited to grow oriented rutile TiO2 nanocones on fluorine doped tin oxide (FTO) under neutral conditions. The examination of phase, crystallinity, morphology, and opto-electronic properties of the well-structured nanocone arrays is characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), ultra violet diffuse reflectance spectroscopy (UV-DRS), Brunnauer-Emmett-Teller (BET) surface area analysis, and field-dependent dark and photoconductivity analysis. The XRD pattern confirms the formation of the tetragonal rutile phase. SEM micrographs and UV-DRS spectroscopy reveals that the length of the nanocones and the energy gap is found to be maximum for 0.04 M concentration with a well-defined excitation band at 316 nm. Significantly, a strong light-trapping effect that decreases the incident light reflections and correspondingly increases the light absorption is unveiled through photoconductive studies for the TiO2 nanocones at 0.04 M having a surface area of 81.767 m2/g. The investigation essentially suggests that the as-prepared one-dimensional nanostructures would serve as efficient photoanodes in environment safe third-generation solar cells.

Metals quantification in e-cigarettes liquids by Total Reflection X-ray Spectrometry.

Electronic cigarettes (e-cig) have gained popularity around the world and its health risks demands more research. This study aims at characterizing e-cig liquids (e-liquids) and its constituents by Total Reflection X-ray Spectrometry (TXRF). The internal standard method was the quantification procedure employed. The spectrometer's performance was evaluated with one certified reference material and spiked samples. It was possible to quantify K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, and Pb in the e-liquids. Concentrations above the limit for potable water were found in 10 out of 38 samples. Principal component analysis was useful for identifying toxic samples. TXRF is a promising technique for e-liquids evaluation due to its simplicity and performance.

[Age prediction based on the examination of bone tissue elemental composition using energy dispersive X-Ray spectroscopy]. / Prognozirovanie vozrasta na osnovanii izucheniya elementnogo sostava kostnoi tkani s pomoshch'yu energodispersionnoi rentgenovskoi spektroskopii.

THE AIM OF THE STUDY: Was to assess the possibility of using chemical analysis of bone mineral content by the means of an energy dispersive X-Ray spectroscopy to determine the age of unidentified corpses for forensic identification. A semi-quantative chemical microanalysis of bone fragments of 85 male and female corpses aged between 21 and 91 was done through the use of energy dispersive X-Ray spectrometer. The association of bone tissue apatite mineral composition with age is confirmed and a formula, connecting age and chemical composition change, is proposed. The possibility of using quantitive evaluation of chemical elements content in the normative mineral to determine the unidentified corpse's age in a standard laboratory, equipped with an energy dispersive X-Ray spectrometer, was proved.

Kß X-ray Emission Spectroscopy of Cu(I)-Lytic Polysaccharide Monooxygenase: Direct Observation of the Frontier Molecular Orbital for H2O2 Activation.

Lytic polysaccharide monooxygenases (LPMOs) catalyze the degradation of recalcitrant carbohydrate polysaccharide substrates. These enzymes are characterized by a mononuclear Cu(I) active site with a three-coordinate T-shaped "His-brace" configuration including the N-terminal histidine and its amine group as ligands. This study explicitly investigates the electronic structure of the d10 Cu(I) active site in a LPMO using Kß X-ray emission spectroscopy (XES). The lack of inversion symmetry in the His-brace site enables the 3d/p mixing required for intensity in the Kß valence-to-core (VtC) XES spectrum of Cu(I)-LPMO. These Kß XES data are correlated to density functional theory (DFT) calculations to define the bonding, and in particular, the frontier molecular orbital (FMO) of the Cu(I) site. These experimentally validated DFT calculations are used to evaluate the reaction coordinate for homolytic cleavage of the H2O2 O-O bond and understand the contribution of this FMO to the low barrier of this reaction and how the geometric and electronic structure of the Cu(I)-LPMO site is activated for rapid reactivity with H2O2.

Towards direct and eco-friendly analysis of plants using portable X-ray fluorescence spectrometry: A methodological approach.

The assessment of the nutritional status of plants is traditionally performed by wet-digestion methods using oven-dried and ground samples. This process requires sampling, takes time, and it is non-environmentally friendly. Agricultural and environmental science have been greatly benefited by in-field, ecofriendly methods, and real-time element measurements. This work employed the portable X-ray fluorescence spectrometry (pXRF) to analyze intact and fresh leaves of crops aiming to assess the effect of water content and leaf surface (adaxial and abaxial) on pXRF results. Also, pXRF data were used to predict the real concentration of macro- and micronutrients. Eight crops (bean, castor plant, coffee, eucalyptus, guava tree, maize, mango, and soybean) with contrasting water contents were used. Intact leaf fragments (∼2 × 2 cm), fresh or oven-dried (60 °C) were obtained to be analyzed via pXRF on both adaxial and abaxial surface. Conventional wet-digestion method was also performed on powdered material to obtain the concentration of macro- and micronutrients via ICP-OES. The data were subjected to descriptive statistics, principal component analysis (PCA) and random forest (RF) algorithm regression. RF was used to predict the real concentration of macro- and micronutrients based on pXRF measurements obtained directly on intact leaves. Water content had a significant effect on pXRF results. However, a positive correlation between the concentration of macro- and micronutrients obtained via pXRF directly on intact leaves and conventional analysis performed on powdered samples was obtained. PCA analysis allowed a clear differentiation of crops based on elemental composition. The concentrations of macro- and micronutrients were very accurately predicted via RF. Even elements not detected by pXRF (N and B) were satisfactory predicted. From this pilot study, it is possible to concluded that pXRF is feasible for in-field assessment of nutritional status of plants. Further studies are needed to obtain specific and robust calibrations for each crop.

BAMline-A real-life sample materials research beamline.

With increasing demand and environmental concerns, researchers are exploring new materials that can perform as well or better than traditional materials while reducing environmental impact. The BAMline, a real-life sample materials research beamline, provides unique insights into materials' electronic and chemical structure at different time and length scales. The beamline specializes in x-ray absorption spectroscopy, x-ray fluorescence spectroscopy, and tomography experiments. This enables real-time optimization of material properties and performance for various applications, such as energy transfer, energy storage, catalysis, and corrosion resistance. This paper gives an overview of the analytical methods and sample environments of the BAMline, which cover non-destructive testing experiments in materials science, chemistry, biology, medicine, and cultural heritage. We also present our own synthesis methods, processes, and equipment developed specifically for the BAMline, and we give examples of synthesized materials and their potential applications. Finally, this article discusses the future perspectives of the BAMline and its potential for further advances in sustainable materials research.

Physiological responses of plants to in vivo X-ray damage from X-ray fluorescence measurements: insights from anatomical, elemental, histochemical, and ultrastructural analyses.

X-ray fluorescence spectroscopy (XRF) is a powerful technique for the in vivo assessment of plant tissues. However, the potential X-ray exposure damages might affect the structure and elemental composition of living plant tissues, leading to artefacts in the recorded data. Herein, we exposed in vivo soybean (Glycine max (L.) Merrill) leaves to several X-ray doses through a polychromatic benchtop microprobe X-ray fluorescence spectrometer, modulating the photon flux density by adjusting either the beam size, current, or exposure time. Changes in the irradiated plant tissues' structure, ultrastructure, and physiology were investigated through light and transmission electron microscopy (TEM). Depending on X-ray exposure dose, decreased K and X-ray scattering intensities and increased Ca, P, and Mn signals on soybean leaves were recorded. Anatomical analysis indicated the necrosis of epidermal and mesophyll cells on the irradiated spots, where TEM images revealed the collapse of cytoplasm and cell wall breaking. Furthermore, the histochemical analysis detected the production of reactive oxygen species and the inhibition of chlorophyll autofluorescence in these areas. Under certain X-ray exposure conditions, e.g. high photon flux density and long exposure time, XRF measurements may affect the soybean leaves structures, elemental composition, and cellular ultrastructure, inducing programmed cell death. Our characterization shed light on the plant's responses to the X-ray-induced radiation damage and might help to establish proper X-ray radiation limits and novel strategies for in vivo benchtop-XRF analysis of vegetal materials.

Structural Characterization of Several Cement-Based Materials Containing Chemical Additives with Potential Application in Additive Manufacturing.

The rapid increase in additive manufacturing applications in all industries has highlighted the lack of innovative technologies and processes in the construction industry. Several European and international policies are in place to guide the development of the technological processes involved in the construction industry toward a sustainable future. Considering the global concerns regarding this industry, the purpose of this study was to develop new cement-based materials that are capable of accelerated hydration and early strength development for use in additive manufacturing. Ca(NO3)2·4H2O, Al2(SO4)3·18H2O and Na2S2O3·5H2O were used to obtain the accelerating effect in the hydration of Portland cement. Based on results obtained from X-ray diffraction (XRD), scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM/EDX) techniques, as well as low-field nuclear magnetic resonance relaxometry (LF-NMR) techniques, it was demonstrated that all accelerators used have a quickening effect on cement hydration. The addition of Na2S2O3·5H2O or combined Na2S2O3·5H2O and Ca(NO3)2·4H2O led to obtaining new cement-based materials with early strength development and fast hydration of microorganized internal structures, critical characteristics for 3D printing.

Visualizing Metal Distribution in Plants Using Synchrotron X-Ray Fluorescence Microscopy Techniques.

Recent improvements in synchrotron-based X-ray fluorescence (SXRF) microscopy established it as an advanced analytical tool for analyzing 2D- and 3D distribution of mineral elements in plants. Among existing imaging techniques, SXRF microscopy offers several unique capabilities, including in situ metal quantification in plant tissues and high sensitivity, as low as 1 mg kg-1, at the nanoscale spatial resolution. SXRF is increasingly utilized in different plant science disciplines to provide a fundamental understanding of metal homeostasis, and the function of trace elements in plant metabolism and development. Here, we describe methods for SXRF imaging, including sample preparation, the optimization of conventional SXRF for analyzing trace elements, and the development of confocal SXRF (C-SXRF).

Distribution of micronutrients in Arborg oat (Avena sativa L.) using synchrotron X-ray fluorescence imaging.

It is important to know the mineral distribution in cereal grains for nutritional improvement or genetic biofortification. Distributions and intensities of micro-elements (Mn, Fe, Cu, and Zn) and macro-elements (P, S, K and Ca) in Arborg oat were investigated using synchrotron-based on X-ray fluorescence imaging (XFI). Arborg oat provided by the Crop Development Center (CDC, Aaron Beattie) of the University of Saskatchewan for 2D X-ray fluorescence scans were measured at the BioXAS-Imaging beamline at the Canadian Light Source. The results show that the Ca and Mn were mainly localized in the aleurone layer and scutellum. P, K, Fe, Cu, and Zn were mainly accumulated in the aleurone layer and embryo. Particularly the intensities of P, K, Cu, and Zn in the scutellum were higher compared to other areas. S was also distributed in each tissue and its abundance in the sub-aleurone was the highest. In addition, the intensities of S and Cu were highest in the nucellar projection of the crease region. All these elements were also found in the pericarp but they were at lower levels than other tissues. Overall, the details of these experimental results can provide important information for micronutrient biofortification and processing strategies on oat through elemental mapping in Arborg oat.

Chemically sprayed CdO: Cr thin films for formaldehyde gas detection and optoelectronic applications.

Chromium (Cr) doped CdO films are chemically sprayed and are characterized by their optical, electrical, structural, and microstructural characteristics. The thickness of the films is determined by spectroscopic ellipsometry. The cubic crystal structure with a superior growth along (111) plane of the spray-deposited films is confirmed from the powder X-ray diffraction (XRD) analysis. XRD studies also suggested that some of the Cd2+ ions were substituted by Cr3+ ions, and the solubility of Cr in CdO is minimal, to be around ∼0.75 wt%. The analysis by atomic force microscopy shows uniform distribution of grains throughout the surface, whose roughness is varied from 33 to 13.9 nm concerning Cr-doping concentration. The microstructures from the field emission scanning electron microscope reveal a smooth surface. The elemental composition is examined using an energy dispersive spectroscope. The micro-Raman studies carried out in room temperature endorse the presence of metal oxide (Cd-O) bond vibrations. Transmittance spectra are obtained using UV-vis-NIR spectrophotometer, and the band gap values are estimated from the absorption coefficient. The films show high optical transmittance (>75%) in vis-NIR region. A maximum optical band gap of 2.35 eV is obtained from 1.0 wt% Cr-doping. The electrical measurement (Hall analysis) confirmed the degeneracy nature and n-type semi-conductivity. The carrier density, carrier mobility, and dc-conductivity are increased for higher Cr-dopant percentage. High mobility (85 cm2V-1s-1) is observed for 0.75 wt% Cr-doping. The 0.75 wt% Cr-doping show a remarkable response to formaldehyde gas (74.39%).

Unlocking the potential of sulphide tailings: A comprehensive characterization study for critical mineral recovery.

Sulphide tailings are a major environmental concern due to acid mine drainage and heavy metal leaching, with costly treatments that lack economic benefits. Reprocessing these wastes for resource recovery can address pollution while creating economic opportunities. This study aimed to evaluate the potential for critical mineral recovery by characterizing sulphide tailings from a Zn-Cu-Pb mining site. Advanced analytical tools, such as electron microprobe analysis (EMPA) and scanning electron microscopy (SEM)-based energy dispersive spectroscopy (EDS), were utilized to determine the physical, geochemical, and mineralogical properties of the tailings. The results showed that the tailings were fine-grained (∼50 wt% below 63 µm) and composed of Si (∼17 wt%), Ba (∼13 wt%), and Al, Fe, and Mn (∼6 wt%). Of these, Mn, a critical mineral, was analyzed for recovery potential, and it was found to be largely contained in rhodochrosite (MnCO3) mineral. The metallurgical balance revealed that ∼93 wt% of Mn was distributed in -150 + 10 µm size fractions containing 75% of the total mass. Additionally, the mineral liberation analysis indicated that Mn-grains were primarily liberated below 106 µm size, suggesting the need for light grinding of above 106 µm size to liberate the locked Mn minerals. This study demonstrates the potential of sulphide tailings as a source for critical minerals, rather than being a burden, and highlights the benefits of reprocessing them for a resource recovery to address both environmental and economic concerns.

Evaluation of enzymatic stamp removal strategies on handmade (cellulose-based) and machine-made (lignin-containing) papers.

Two different biocleaning techniques for stamp removal from different paper samples (handmade and machine-made) were investigated. Cellulose is the main component of handmade paper, while higher concentration of lignin is present in machine-made paper. Biocleaning methods included the direct application on paper surfaces of the extracellular enzymatic mixture (EEM) extracted from the yeast Sporidiobolus metaroseus and the recombinant protein CthediskatG of Chaetomium thermophilum var. dissitum. The produced microbial enzymes (EEM or CthediskatG) were also combined with agarose hydrogels. The effectiveness of the cleaning ability of the individual methods was determined using different spectrophotometer measurements based on colorimetric analysis and by Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR). Some tested samples were also subjected to microstructural and chemical analysis using Scanning Electron Microscope-Energy-Dispersive X-ray spectroscopy (SEM-EDX). The analysis showed that the EEM-based approaches were the most suitable, mainly they are less time-consuming and easy to produce, and moreover slight differences were displayed between EEM and CthediskatG during the removal of the stamp by hydrogel-enzyme approaches. Both EEM applications (direct and hydrogel) speed up the stamp removal process from real paper samples. However, for the complete elimination of the stamp smears a quick N,N-dimethylformamide post-treatment is advised too.

Bone lead variability in bone repository skeletal samples measured with portable x-ray fluorescence.

Bone lead serves as a better, more accessible biomarker to many communities experiencing chronic exposure to lead. A new method using low energy x-ray fluorescence in a handheld device (portable XRF) allows us to measure this chronic biomarker in only a few minutes. However, many unknowns remain about this biomarker measured using a new low energy x-ray technique. The low energy of the new method was theorized to measure a slightly different portion of the bone than previous techniques, which could influence measurements at different bone sites and types. We tested how bone measurements varied across five bone sites: mid-tibial shaft, proximal tibia, distal tibia (ankle), ilium, and cranium. We found bone lead measurements are not significantly different between skeletal elements when measured using a portable XRF. On average, bone lead in the repository samples was measured to be 21.6 ± 21.3 µg/g with an XRF detection limit of 2.1 ± 0.5 µg/g. Cumulative lead exposure can be effectively measured using the portable XRF on a variety of bone types, but the tibia should be preferentially measured to compare between studies and individuals.

Effect of different aging treatments on the transport of nano-biochar in saturated porous media.

Widely used for soil amendment, carbon sequestration, and remediation of contaminated soils, biochars (BCs) inevitably produce a large number of nanoparticles with relatively high mobility. Geochemical aging alters chemical structure of these nanoparticles and thus affect their colloidal aggregation and transport behavior. In this study, the transport of ramie derived nano-BCs (after ball-milling) was investigated by different aging treatments (i.e., photo (PBC) and chemical aging (NBC)) as well as the managing BC under different physicochemical factors (i.e., flow rates, ionic strengths (IS), pH, and coexisting cations). Consequences of the column experiments indicated aging promoted the mobility of the nano-BCs. Compared to the nonaging BC, consequences of spectroscopic analysis demonstrated the aging BCs exhibited a number of tiny corrosion pores. Both of these aging treatments contribute to a more negative zeta potential and a higher dispersion stability of the nano-BCs, which is caused by the abundance of O-functional groups. Also the specific surface area and mesoporous volume of both aging BCs increased significantly, with the increase being more pronounced for NBC. The breakthrough curves (BTCs) obtained for the three nano-BCs were modelled by the advection-dispersion equation (ADE), which included first-order deposition and release terms. The ADE revealed high mobility of aging BCs, which meant their retention in saturated porous media was reduced. This work contributes to a comprehensive understanding of the transport of aging nano-BCs in the environment.

The use of synchrotron X-ray fluorescent imaging to study distribution and content of elements in chemically fixed single cells: a case study using mouse pancreatic beta-cells.

Synchrotron X-ray fluorescence microscopy (SXRF) presents a valuable opportunity to study the metallome of single cells because it simultaneously provides high-resolution subcellular distribution and quantitative cellular content of multiple elements. Different sample preparation techniques have been used to preserve cells for observations with SXRF, with a goal to maintain fidelity of the cellular metallome. In this case study, mouse pancreatic beta-cells have been preserved with optimized chemical fixation. We show that cell-to-cell variability is normal in the metallome of beta-cells due to heterogeneity and should be considered when interpreting SXRF data. In addition, we determined the impact of several immunofluorescence (IF) protocols on metal distribution and quantification in chemically fixed beta-cells and found that the metallome of beta-cells was not well preserved for quantitative analysis. However, zinc and iron qualitative analysis could be performed after IF with certain limitations. To help minimize metal loss using samples that require IF, we describe a novel IF protocol that can be used with chemically fixed cells after the completion of SXRF.

Soybean sorting based on protein content using X-ray fluorescence spectrometry.

The purpose of this research was to evaluate performance of an energy-dispersive X-ray fluorescence (XRF) sensor to classify soybean based on protein content. The hypothesis was that sulfur signals and other XRF spectral features can be used as proxies to infer soybean protein content. Sample preparation and equipment settings to optimize detection of S and other specific emission lines were tested for this application. A logistic regression model for classifying soybean as high- or low-protein was developed based on XRF spectra and protein contents. Additionally, the model was validated with an independent set of samples. Global accuracies of the method were 0.83 (training set) and 0.81 (test set) and the corresponding kappa indices were 0.66 and 0.61, respectively. These numbers indicated satisfactory performance of the sensor, suggesting that XRF spectral features can be applied for screening protein content in soybean.

Use of scanning electron microscopy and energy dispersive X-ray spectroscopy to identify key fouling species during alternating tangential filtration.

Alternating tangential flow filtration (ATF) has become one of the primary methods for cell retention and clarification in perfusion bioreactors. However, membrane fouling can cause product sieving losses that limit the performance of these systems. This study used scanning electron microscopy and energy dispersive X-ray spectroscopy to identify the nature and location of foulants on 0.2 µm polyethersulfone hollow fiber membranes after use in industrial Chinese hamster ovary cell perfusion bioreactors for monoclonal antibody production. Membrane fouling was dominated by proteinaceous material, primarily host cell proteins along with some monoclonal antibody. Fouling occurred primarily on the lumen surface with much less protein trapped within the depth of the fiber. Protein deposition was also most pronounced near the inlet/exit of the hollow fibers, which are the regions with the greatest flux (and transmembrane pressure) during the cyclical operation of the ATF. These results provide important insights into the underlying phenomena governing the fouling behavior of ATF systems for continuous bioprocessing.

Myogenesis and Analysis of Antimicrobial Potential of Silver Nanoparticles (AgNPs) against Pathogenic Bacteria.

The widespread and indiscriminate use of broad-spectrum antibiotics leads to microbial resistance, which causes major problems in the treatment of infectious diseases. However, advances in nanotechnology have opened up new domains for the synthesis and use of nanoparticles against multidrug-resistant pathogens. The traditional approaches for nanoparticle synthesis are not only expensive, laborious, and hazardous but also have various limitations. Therefore, new biological approaches are being designed to synthesize economical and environmentally friendly nanoparticles with enhanced antimicrobial activity. The current study focuses on the isolation, identification, and screening of metallotolerant fungal strains for the production of silver nanoparticles, using antimicrobial activity analysis and the characterization of biologically synthesized silver nanoparticles by X-ray diffraction (XRD) spectroscopy, energy-dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM). In total, 11 fungal isolates were isolated and screened for the synthesis of AgNPs, while the Penicillium notatum (K1) strain was found to be the most potent, demonstrating biosynthetic ability. The biologically synthesized silver nanoparticles showed excellent antibacterial activity against the bacteria Escherichia coli (ATCC10536), Bacillus subtilis, Staphylococcus aureus (ATCC9144), Pseudomonas aeruginosa (ATCC10145), Enterococcus faecalis, and Listeria innocua (ATCC13932). Furthermore, three major diffraction peaks in the XRD characterization, located at the 2θ values of 28.4, 34.8, 38.2, 44, 64, and 77°, confirmed the presence of AgNPs, while elemental composition analysis via EDX and spherical surface topology with a scanning electron microscope indicated that its pure crystalline nature was entirely composed of silver. Thus, the current study indicates the enhanced antibacterial capability of mycologically synthesized AgNPs, which could be used to counter multidrug-resistant pathogens.

Nondestructive characterization of diseased Chinese chive leaves using X-ray intensity ratios with microbeam synchrotron radiation X-ray fluorescence spectrometry.

The Chinese chive (Allium tuberosum) is a core crop grown in Kochi Prefecture, Japan. However, withering symptoms occur during greenhouse growing, which have a negative impact on crop management Chinese chive leaves with physiological disorders (PD) or necrotic streak disease (ND) present with withering as typical blight symptoms. Excess or deficiency of elements may cause such withering in Chinese chive leaves with PD. Therefore, visualizing the elemental distribution in plant bodies may help clarify the cause of this withering. In this study, using synchrotron radiation X-ray fluorescence (SR-XRF) imaging, we examined the elemental distribution conditions in healthy Chinese chive leaves without withering, those that withered due to PD, and those that withered due to ND. Segmentation analysis of inductively coupled plasma-optical emission spectroscopy (ICP-OES) was performed on the SR-XRF imaged Chinese chive leaves and the data from the two analytical methods were compared. SR-XRF imaging provided more detailed data on elemental distribution compared with segmentation analysis using ICP-OES. Based on the SR-XRF imaging results, the X-ray intensity ratios for Ca/K, Fe/Mn, and Zn/Cu were calculated. These findings support that the Ca/K, Fe/Mn, and Zn/Cu X-ray intensity ratios can be used in the early detection of withered leaves and to predict the factors causing withering.