Functional osseoconductive coatings based on hydroxylapatite (HAp) and applied preferentially by atmospheric plasma spraying to medical implant surfaces are a mainstay of modern implantology. During contact with the hot plasma jet, HAp particles melt incongruently and undergo complex dehydration and decomposition reactions that alter their phase composition and crystallographic symmetry, and thus, the physical and biological properties of the coatings. Surface analytical methods such as laser-Raman and nuclear magnetic resonance (NMR) spectroscopies are useful tools to assess the structural changes of HAp imposed by heat treatment during their flight along the hot plasma jet. In this contribution, the controversial information on the existence or non-existence of oxyapatite, i.e. fully dehydrated HAp as a thermodynamically stable compound is highlighted.

Two-dimensional (2D) semiconductors like Transitional Metal Dichalcogenides (TMDCs) have attracted strong research interest in the last decade. Unlike the more celebrated 2D material graphene, TMDCs like molybdenum disulfide(MoS₂) possess bandgap. The number of layers critically depends on the band structure of MoS₂. For example, it is indirect for bulk MoS₂. However, it becomes direct bandgap material for a monolayer MoS₂. Monolayer MoS₂, therefore, becomes an important material for photoelectronic devices. An essential aspect of such devices is the metal-semiconductor junction. Metal-TMDC junction is, therefore, a well-studied interface due to its importance for 2D materials-based photoelectronic devices. Most importantly, it can be flexible, stretchable to it’s length, and bent to a large angle. We used metals like Au and Al to interface with TMDs like MoS₂. We used silicon and PDMS as substrates. So, we have to focus on investigating the relative properties of various TMDCs. We see change in band energy and vibrational modes via Photoluminiscence and Raman spectroscopy as shown in the article. However, certain aspects are yet to be explored, for example, how this interface behaves in the presence of strain.

: Dacarbazine, DAC, 5-(3,3-dimethyltriazeno)imidazol-4-carboxamideis is an imidazole-carboxamide derivative, that is structurally related to purines. DAC belongs to the triazene compounds, which are a group of alkylating agents with antitumour and mutagenic properties. DAC is a non-cell cycle specific drug, active on all phases of cellular cycle. In the frame of this work the 3d-metal complexes (cobalt and copper) with dacarbazine were synthesized. Their spectroscopic properties by the use of FT-IR, FT-Raman and 1HNMR were studied. The structures of dacarbazine and its complexes with copper(II) and cobalt(II) were calculated using DFT methods. The effect of metals on the electronic charge distribution of dacarbazine was discussed on the basis of calculated NBO atomic charges. The reactivity of metal complexes in relation to ligand alone was estimated on the basis of calculated energy of HOMO and LUMO orbitals. The aromaticity of imidazole ring in dacarbazine and the complexes was compared (on the basis of calculated geometric indices of aromaticity). Thermal stability of the investigated 3d-metal complexes with dacarbazine and the products of their thermal decomposition were analyzed.

Recognition, decoding and tracking of vortex patterns is of increasing importance in many fields reaching from astronomical observation of distant galaxies to turbulence phenomena in liquids or gases. Currently, coherent light beams with orbital angular momentum (OAM) are of particular interest for optical communication, metrology, micro-machining or particle manipulation. One common task is to identify characteristic spiral patterns in pixelated intensity maps at real-world signal-to-noise ratios. Recently, Fast Fourier Transform (FFT) was applied to the quantitative analysis of spiral interference patterns of OAM beams. Our study considers this approach in more detail. It is demonstrated that specific information can be extracted by combining conformal mapping by polar transform with determining one- or two-dimensional angular frequency spectra either in spatially fixed or scanning mode. Results of proof-of-principle experiments are presented.

Orientational dependence of the IR absorbing amide bands of silk is demonstrated from two orthogonal longitudinal and transverse microtome slices only $\sim 100$~nm thick. A scanning near-field optical microscopy (SNOM) which preferentially probes orientation perpendicular to the sample's surface was used. Spatial resolution of silk-epoxy boundary was defined with a $\sim 100$~nm resolution while the spectra were collected by a $\sim 10$~nm tip. Ratio of the absorbance of the amide-II C-N at 1512~cm$^{-1}$ and amide-I C=O $\beta$-sheets at 1628~cm$^{-1}$ showed sensitivity of SNOM to the molecular orientation. SNOM characterisation is complimentary to the far-field absorbance which is sensitive to the in-plane polarisation. Volumes with cross sections smaller than 100~nm can be characterised for molecular orientation. A method of absorbance measurements at four angles of slice cut orientation, which is equivalent to the four polarisation angles absorbance measurement is proposed.

Blood testing is a crucial application in the field of clinical studies for disease diagnosis and screening, biomarkers discovery, organ function assessment, and personalized medication. Therefore, it is of utmost importance to collect precise data in a short time. In this study, we utilized Raman spectroscopy to analyze blood samples and extracted comprehensive biological information, including the primary components and compositions present in the blood. We conducted short-wavelength (532 nm green light) Raman scattering spectroscopy on blood samples, plasma, and serum, and subsequently analyzed the biological characteristics detected in each sample type. Our results indicated that whole blood had high hemoglobin content, which suggests that hemoglobin is a major component of blood. The characteristic Raman peaks of hemoglobin were observed at 690, 989, 1015, 1182, 1233, 1315, and 1562–1649 cm−1. Analysis of plasma and serum samples indicated the presence of β-carotene, which exhibited characteristic peaks at 1013, 1172, and 1526 cm−1. Additionally, in the field of medical blood testing, the novel 3D Silicon micro-channel device technology holds immense potential. It can serve as a substrate and helps to detect various diseases and biomarkers, providing real-time data to help medical professionals and patients better understand their health conditions. Changes in biological data collected in this manner could potentially be used to diagnose clinical diseases.

Employment implies economic independence, social inclusion, non-discrimination and impacts people’s life in areas beyond work. Therefore, for persons with disabilities (PwD), that include persons with chronic diseases (PwCD), equal employment opportunities must be provided and reasonable accommodation (RA) in employment carefully designed. The objectives of this study done in Slovenia were: (i) to translate and adapt RA Factor Survey (RAFS; Dong et al., 2010); (ii) to examine psychometric properties of its expanded Slovenian modification Aspects of RA survey (ARAS); (iii) to find out the views of professionals in the field by ARAS; (iv) to present Slovenian model of employment rehabilitation concerning PwD and PwCD. ARAS was developed with the collaboration of professionals performing focus groups, it consists of three parts Influencing factors, Contents areas and Barriers with 78 items. Data were collected from 140 professionals and underwent descriptive statistics and factor analysis. The results showed that the key factors for RA implementation are attitude and support of employer/organization. Other important factors are employee and his/her employment, the conditions to implement RA, and the awareness of employee and work environment. ARAS might be used as a framework to assist in the development, improvement, and implementation of RA in practice. This is discussed in the broader context of equal opportunities for employment of PwD including PwCD and the welfare model in Slovenia.

Micro- and nanoflowers are a class of materials composed of particles with high surface-to-volume ratio. They are being extensively studied in the last decade due to simple preparation protocols and promising applications in biosensing, as drug delivery agents, for water purification and so on. Flowerlike objects, due to their highly irregular surface, may act also as plasmonic materials, providing resonant coupling between optical waves and surface plasmon excitations. This fact infers for the possibility to use micro- and nanoflowers as effective surface-enhanced Raman scattering (SERS) substrate materials. Here, we report on the design and Raman enhancement properties of silver flowerlike structures, deposited on aluminum surface. A simple and cost-effective fabrication method is described, which leads to SERS substrates of high developed surface area. The morphology of the silver flowers on a nanoscale is characterized by self-organized quasiperiodic stacks of nanosheets, which act as plasmonic cavity-resonators. The substrates were tested against rhodamine-6G (R6G) water solutions of concentration varying between 10^–3 M and 10^–7 M. Optimal SERS enhancement factors of up to 10⁵ were established at R6G concentrations in the range 10^–6 – 10^–7 M.

Peptides, both natural and synthetic, are well suited for a wide range of purposes and offer versa-tile applications in different fields such as biocatalysts, injectable hydrogels, tumor treatment, and drug delivery. The rising prominence of therapeutic peptides encompasses anticancer, antiviral, antimicrobial, and anti-neurodegenerative properties. The metals Na, K, Mg, Ca, Fe, Mn, Co, Cu, Zn, and Mo are ten of the twenty elements that are considered essential for life. Crucial for under-standing the biological role of metals is the exploration of metal-bound proteins and peptides. Aside from essential metals, there are other, non-essential metals that also interact biologically, exhibiting either therapeutic or toxic effects. Irregularities in metal binding contribute to diseases like Alzheimer’s, neurodegenerative disorders, Wilson's, and Menkes disease. Certain metal com-plexes have potential applications as radiopharmaceuticals. The examination of these complexes was done by preforming UV-Vis, IR, EPR, NMR spectroscopy, and X-ray analysis.

In this paper, we aim to present real implementation cases where non-visible elements of environmental impact assessments (EIA), wind flow, are visualized using a 3D digital twin technology. The conventional EIA process serves as a crucial tool in the evaluation of potential environmental impacts prior to the initiation of development projects. This evaluation helps to establish a legal and institutional framework that seeks to minimize the adverse effects on the environment. However, traditional EIA methods present challenges, particularly for non-experts, in comprehending the results of assessments involving non-visible environmental factors such as noise, air quality, and wind flow. These elements are often represented in static images or numerical tables, limiting accurate understanding and engagement. Our proposed method, termed Digital Twin based EIA, addresses these limitations by leveraging digital twin technology. This advanced methodology allows for the visualization of non-visible environmental elements in a spatio-temporal dimension, providing a more interactive and comprehensive user interface/experience for both citizens and stakeholders. In this context, we present a unique case study that focuses on visualizing wind flow using this technology. This paper serves as an example of how digital twin platforms can enhance traditional EIA processes, offering a more immersive and informative experience. The evolution of EIA into the digital realm signifies an important step forward in fostering public understanding and engagement in environmental protection efforts.

Crystalline silver thin layers were obtained by high-energy pulsed laser ablation without heating of the deposition substrate. The fluid Plateau-Rayleigh (PRI), Rayleigh – Taylor (RTI) and Richtmyer – Meshkov (RMI) instabilities, as well as crown splash induced during pulsed laser deposition (PLD) in high energy regime, resulting in ring and pearl shaped structures, offer the benefit of increased sorption surface. These morphological structures obtained for the silver thin layers make them of interest for catalytic applications. The study presented with this work addresses both the fundamental and applied issues on the morphological structures obtained for the silver thin layer and their catalytic function in organic processes. In this sense, the catalytic action of the thin silver layer was highlighted by modifications of the Reactive Blue 21 dye (C.I.) in aqueous solution with sodium bicarbonate. Specific investigations and analyzes were carried out by electron microscopy and elemental analysis (SEM-EDX), atomic force microscopy (AFM) and profilometry, mass spectrometry, ablation plasma diagnosis, diffractograms (XRD), as well as IR spectroscopy (FTIR). In addition to the experimental investigation and analyzes, simulation of the ionization energy threshold was conducted in COMSOL for complementary evaluation on the involved processes and phenomena.

The fine structure of Apricot pectin polysaccharides is discussed from both literature and recent work we have performed. Structural characterization utilized 1D and 2D homo- and hetero-nuclear NMR spectroscopy including results from High Performance Size Exclusion Chromatography (HP-SEC), HP Anion-Exchange Chromatography with Pulsed Amperometric Detection (HPAEC-PAD) and FTIR spectroscopy. The purified pectin fraction (F1AP) was found to be composed of D-galacturonic acid, L-rhamnose, D-arabinose and D-galactose in a 1.0 : 0.1 : 0.36 : 0.12 molar ratio, respectively, which is consistent with a pectin RG-1 branched with arabinogalactan side chain polysaccharides, and has a weight-average molecular weight of approximately 1588.2 kDa. The slope of the hydrodynamic radius versus the molar mass was 0.57, indicating the presence of coil conformations. The results from HPAEC-PAD, HPSEC and NMR spectroscopy (1H, 13C, zTOCSY, HSQC, HSQCTOXY and HMBC) demonstrated that F1AP fine fraction F1AP1, derived from original F1AP, has a backbone of (1→4)-linked -D-galacturonic acid and -L-rhamnopyranosyl residues branched with arabinogalactan of multiply glycosidic linkages of T- α-Araf, 3-α-Araf, 5-α-Araf, T- α -Arap, 2- α-Arap side chains, having methyl and acetylated groups, and has high molecular weights (1945 kDa). While the other F1A6 fraction consists predominately of an HG region of pectin polysaccharides with low molecular weights (117.5 kDa), less aggregated. The F1AP1 polysaccharide was highly viscous and its hydrodynamic radius was 64,3 nm. The exponent b of Rh-Mw (conformation plot) was determined to be 0.48, indicating a compact flexible coil conformation of the macromolecule in solution. However, the F1AP6 fraction of apricot fruits belong to backbone of repeats units of [-(1→4)-α-D-GalpA-1]n – both HG and partly contents RG-II polysaccharides, bearing heterosugar sidechains, including α-Ara, α -Rha and β-Gal residues and adopt more stiffness rod like conformation.

Biological nitrogen fixation (BNF) by symbiotic bacteria plays a vital role in sustainable agriculture. However, current quantification methods are often expensive and impractical. This study explores the potential of Raman spectroscopy, a non-invasive technique, for rapid assessment of BNF activity in soybeans. Raman spectra were obtained from soybean plants grown with and without rhizobia bacteria to identify spectral signatures associated with BNF. δN15 isotope ratio mass spectrometry (IRMS) was used to determine actual BNF percentages. Partial least squares regression (PLSR) was employed to develop a model for BNF quantification based on Raman spectra. The model explained 80% of the variation in BNF activity. To enhance the model's specificity for BNF detection regardless of nitrogen availability, a subsequent elastic net (Enet) regularization strategy was implemented. This approach provided insights into key wavenumbers and biochemicals associated with BNF in soybeans.

The indole nucleus is an important element of many natural and synthetic molecules with significant biological activity. Nonetheless, the co-presence of transitional metals in organic scaffold may represent an important factor in the development of effective medicinal agents. This review covers some of the relevant and recent achievements in the biological, chemical and pharmacological activity of important indole-based metal complexes in the area of drug discovery.

Topoisomerases, common targets for anti-tumor therapeutics, are crucial enzymes for DNA replication, transcription, and many other aspects of DNA metabolism. The potential anti-cancer effect of thiosemicarbazones (TSC) and metal-TSC complexes has been demonstrated by targeting several biological processes, including DNA metabolism. Human topoisomerases were discovered among the molecular targets for TSCs, and metal-chelated TSCs specifically displayed significant inhibition. The processes by which metal-TSCs or TSCs inhibit topoisomerases are still being studied. In this brief review, we summarize the TSCs and metal-TSCs that inhibit various types of human topoisomerases.

Multinuclear NMR studies of the gaseous mixtures that involve volatile compounds and ³He atoms are featured in this review. Precise analyses of the ³He and other nuclei resonance frequencies show linear dependences on the gas density. Extrapolation of the gas phase results to the zero-pressure limit gives ν₀(³He) and ν₀(ⁿX) resonance frequencies of nuclei in a single 3-helium atom and nuclei in molecules at a given temperature. The NMR frequency comparison method provides an approach for determining different nuclear magnetic moments. Application of quantum chemical shielding calculations which include a more complete and careful theoretical treatment allows the shielding of isolated molecules to be achieved with great accuracy and precision. They are used for evaluation of nuclear moments without shielding impact on bare nuclei: ^10/11B, ¹³C, ¹⁴N, ¹⁷O, ¹⁹F, ²¹Ne, ²⁹Si, ³¹P, ³³S, ^35/37Cl, ³³S , ⁸³Kr, ^129/131Xe, and ¹⁸³W. On the other hand, new results of nuclear moments were used for reevaluation of absolute nuclear magnetic shielding in molecules under study. Additionally, ³He gas in water solutions of lithium and sodium salts was used for measurements of ^6/7Li and ²³Na magnetic moments and reevaluation of shielding parameters of Li⁺ and Na⁺ water solvated cations. In this paper, guest ³He atoms that play a role in probing the electron density in many host macromolecules are presented as well.

Low-frequency peaks in the Raman spectra of amorphous poly (ether ketone) (PEEK) are investigated. An amorphous sample with zero crystallinity, as confirmed by WAXRD, was used in this study. In a previous study, two peaks were observed in the low-frequency Raman spectra of crystallized samples. One of the peaks at 135 cm-1, disappeared for the amorphous sample. Furthermore, the peak at 50 cm-1 was observed for the first time in the crystallized sample. The peak at 50 cm-1, similar to the peak at 135 cm-1, disappeared in the amorphous state, and its intensity increased with increasing crystallinity. The origins of the two peaks were both associated with the Ph-CO-Ph-type intermolecular vibrational modes in the simulation. It was suggested that the Ph-CO-Ph vibrational mode observed in the low-frequency region of PEEK was strongly in-fluenced by the intermolecular order.

Optofluidics, a research discipline combining optics with microfluidics, currently aspires to revolutionize the analysis of biological and chemical samples e.g. for medicine, pharmacology, or molecular biology. In order to detect low concentrations of analytes in water, we developed an optofluidic device containing a nanostructured substrate for surface enhanced Raman spectroscopy (SERS). The geometry of the gold surface allows localized plasmon oscillations to give rise to the SERS effect, in which the Raman spectral lines are intensified by the interaction of the plasmonic field with the electrons in the molecular bonds. The SERS substrate was enclosed in a microfluidic system, which allowed transport and precise mixing of the analyzed fluids, while preventing contamination or abrasion of the highly sensitive substrate. To illustrate its practical use, we employed the device for quantitative detection of persistent environmental pollutant 1,2,3-trichloropropane in water in submillimolar concentrations. The developed sensor allows fast and simple quantification of halogenated compounds and it will contribute towards the environmental monitoring and enzymology experiments with engineered haloalkane dehalogenase enzymes.

Analyzing the cells in various body fluids can greatly deepen the understanding of the mechanisms governing the cellular physiology. Because of the variability of physiological and metabolic states, it is important to be able to perform such studies on individual cells. Therefore, we developed an optofluidic system in which we precisely manipulated and monitored individual cells of Escherichia coli. We used laser tweezers Raman spectroscopy (LTRS) in a microchamber chip to manipulate and analyze individual E. coli cells. We subjected the cells to antibiotic cefotaxime, and we observed the changes by the time-lapse microscopy and Raman spectroscopy. We found observable changes in the cellular morphology (cell elongation) and in Raman spectra, which were consistent with other recently published observations. We tested the capabilities of the optofluidic system and found it to be a reliable and versatile solution for this class of microbiological experiments.

In this work, we obtained three new phosphorescent iridium complexes (Ir1-Ir3) of general stoichiometry [Ir(N^C)2(N^N)]Cl decorated with oligo(ethylene glycol) fragments to make them water soluble and biocompatible, as well as to protect them from aggregation with biomolecules such as albumin. The major photophysical characteristics of these phosphorescent complexes are determined by the nature of two cyclometallating ligands (N^C) based on 2-pyridine-benzothiophene, since quantum chemical calculations revealed that the electronic transitions responsible for the excitation and emission are localized mainly at these fragments. However, the use of various diimine ligands (N^N) proved to affect the quantum yield of phosphorescence and allows for changing the complexes sensitivity to oxygen, due to the variations in the steric accessibility of the chromophore center for O2 molecules. It was also found that the N^N ligands made possible to tune the biocompatibility of the resulting compounds. The wavelengths of the Ir1-Ir3 emission maxima fall in the range of 630-650 nm, the quantum yields reach 17% (Ir1) in deaerated solution and sensitivity to molecular oxygen, estimated as ratio of emission lifetime in deaerated and aerated water solution, displays the highest value 8.2 for Ir1. The obtained complexes feature low toxicity, good water solubility and the absence of a significant effect of biological environment components on the parameters of their emission. Of the studied compounds Ir1 and Ir2 have been chosen for in vitro and in vivo biological experiments aimed at estimation of oxygen concentration in cell lines and tumors. These sensors have demonstrated their effectiveness for mapping the distribution of oxygen and for monitoring hypoxia in biological objects studied.

In this article, we delve into the intricate behavior of electronic mechanisms underlying NMR magnetic shieldings, σ, in molecules containing heavy atoms such as cadmium, platinum, and mercury. Specifically, we explore PtXn^{−2} (X = F, Cl, Br, I; n = 4, 6) and XCl2 Te2 Y2 H6 (X = Cd, Hg; Y = N, P) molecular systems. It is known that the leading electronic mechanisms responsible for the relativistic effects on σ are well characterized by the linear response with elimination of small components model (LRESC). In this study, we present results obtained from the innovative LRESC-Loc model, which offers the same outcomes as the LRESC model but employs localized molecular orbitals (LMOs) instead of canonical MOs. These LMOs provide a chemist’s representation of atomic core, lone pairs, and bonds. The whole set of electronic mechanisms responsible of the relativistic effects can be expressed in terms of both non-ligand-dependent and ligand-dependent contributions. We elucidate the electronic origins of trends and behaviors exhibited by these di- verse mechanisms in the aforementioned molecular systems. In PtX4^{−2} molecules, the predominant relativistic mechanism is the well-established one-body spin-orbit (σ^SO(1) ) mechanism, while the paramagnetic mass-velocity (σ^Mv ) and Darwin (σ^Dw ) contributing mechanisms also demand con- sideration. However, in PtX6−2 molecules, the σ Mv+ Dw contribution surpasses that of the SO(1) mechanism, thus influencing the overall ligand-dependent contributions. As for complexes con- taining Cd and Hg, the ligand-dependent contributions exhibit similar magnitudes when nitrogen is substituted with phosphorus. The only discrepancy arises from the σ^SO(1) contribution, which changes sign between the two molecules due to the contribution of bond orbitals between the metal and tellurium atoms.

This review summarizes experimental and theoretical studies of transition metal complexes with two types of novel metal-carbon bonds. One type features complexes with carbones CL2 as ligands, where the carbon(0) atom has two electron lone pairs which engage in double (σ and π) donation to the metal atom [M] CL2. The second part of this review reports complexes which have a neutral carbon atom C as ligand. Carbido complexes with naked carbon atoms may be considered as endpoint of the series [M]-CR3 → [M]-CR2 → [M]-CR → [M]-C.

In this study, Raman spectroscopy is employed to investigate the chemical compounds of kumquat peels and compared that of orange. Kumquat is a citrus fruit belonging to the genus Fortunella in family Rutaceae. It is observed that kumquat peel has 3 main Raman active characteristic vibration modes specified to carotenoids, which is dominated by β-carotene at 1007, 1158 and 1526 cm-1, as it is well known for orange. The carotenoid distribution within the cross-section of kumquat is also investigated. The carotenoid-related Raman vibration modes are relatively stronger on the peel of kumquat, which is an important finding especially for the fruits that can be eaten with its peel. Our results pave the way to take an attention for the importance of kumquat as being a fruit that can be grown up in different climates compared to orange, which grow in warm climates.

Prevalence of antimicrobial-resistant bacteria has become a major challenge worldwide. Methicillin-resistant Staphylococcus aureus (MRSA)—a leading cause of infections—forms biofilms on polymeric medical devices and implants, increasing their resistance to antibiotics. Antibiotic administration before biofilm formation is crucial. Raman spectroscopy was used to assess MRSA biofilm development on solid culture media from 0 to 48 h. Biofilm formation was monitored by measuring DNA/RNA-associated Raman peaks and protein/lipid-associated peaks. The search for an antimicrobial agent against MRSA biofilm revealed that Eugenol was a promising candidate as it showed significant potential for breaking down the biofilm. Eugenol was applied at different times to test the optimal time for inhibiting MRSA biofilms, and the Raman spectrum showed that the first 5 h of biofilm formation was the most antibiotic-sensitive time. This study investigated the performance of Raman spectroscopy coupled with Principal Component Analysis (PCA) to identify planktonic bacteria from biofilm conglomerates. Raman analysis, microscopic observation, and quantification of the biofilm growth curve indicated early adhesion from 5 to 10 h of incubation time. Therefore, Raman spectroscopy can help in monitoring biofilm formation on a solid culture medium and performing rapid antibiofilm assessments with new antibiotics during the early stages of the procedure.

We have investigated the influence of the relative proportions of glass formers in a series of lithium alumino-borosilicate glasses with respect to electrical conductivity () and glass transition temperature (Tg) as functions of glass structure, as determined by Raman spectroscopy. The ternary lithium alumino-borate glass exhibits the highest  and lowest Tg among all the compositions of the glass series, 30Li2O•3Al2O3• (67-x) B2O3•xSiO2. However, as B2O3 is replaced by SiO2, a shallow minimum in  as well as a shallow maximum in Tg are observed near x = 27, where the Raman spectra indicate isolated diborate/tetraborate/orthoborate groups are being progressively replaced by danburite/reedmergnerite-like borosilicate network units. Overall, as the glasses become silica-rich,  is minimized, while Tg is maximized. In general, these findings show correlations among Tg, (sensitive to network polymerization),  (proportional to ionic mobility), and the different borate and silicate glass structural units as determined by Raman spectroscopy. X-ray diffraction analyses demonstrate the absence of appreciable crystallinity in the glasses investigated. However, scanning electron microscopy (SEM) images of HF-etched samples showed that glasses, and especially the borate-rich compositions comprise two distinct glassy phases. The isolated phase is 25-100 nm in diameter, dispersed evenly in a glassy matrix.

Aim of the presented research was to develop an optical sensing system to investigate the demineralization process of the bones. Optical measurement techniques are widely used and increasingly adapted in biological and biomedical applications due to their non-destructive nature and safety. Optical examination of the bone condition could facilitate clinical trials and improve the safety of patients. The authors used a set of complementary methods: polarization-sensitive optical coherence tomography (PS-OCT) and Raman spectroscopy. To stimulate the process of demineralization and gradual removal of the hydroxyapatite, the test samples of chicken bones were placed into 10% acetic acid. Measurements were carried out in two series. The first one took two weeks with data acquired every day. In the second series, the measurements were made during one day at an hourly interval (after 1, 2, 3, 5, 7, 10, and 24 hours). Raman spectroscopy was used to evaluate the disappearance of the hydroxyapatite. The relation between the content of hydroxyapatite and images recorded using OCT was analyzed and discussed. Moreover, the polarization properties of the bones have been evaluated. Based on OCT images, the retardation angles of the bones have been calculated. This work presents a preliminary study on the mechanism of bone demineralization and confirms the potential of the applied optical methods.

Biosolids from stabilized sludge presents a high fertilization potential due to its rich content of nutrients and organic matter. Three formulas of organo-mineral fertilizers based on biosolids were manufactured having at least 2 % N, 2 % P2O5, and 2 % K2O and characterized by classical and advanced methods. The content of N and P in the final formula was measured using specific reactants combined with VIS-nearIR spectroscopy. Additionally, all three formulas were characterized by advanced 1H NMR relaxometry, double-quantum and FT-IR spectroscopy. Structural characterization was performed using SEM, EDX and X-ray diffraction. Four dynamical components were identified in the T2-distribution showing that the rigid component is into a percentage larger than 90 %. In order to evaluate the release properties of organo-mineral fertilizers dynamic measurements of electric conductivity and pH were performed, by placing 0.25 g of formulas (V1, V2 and V3) in 200 ml of distillate water. It was found that V3 present the smallest release velocity, but release the largest amount of fertilizers. Two release mechanisms were also observed.

Based on the electron-deficient property of picric acid (PA), two neutral Ir(III) complexes 1 and 2 modified with the electron-rich carbazolyl groups were synthesized and characterized. Both 1 and 2 exhibit aggregation-induced phosphorescence emission (AIPE) properties in THF/H2O. Among them, 2 is extremely sensitive for detecting PA with a limit of detection of 0.15 μM in THF/H2O. Furthermore, the selectivity for PA is significantly higher compared to other analytes, enabling efficient detection of PA in four common water samples. The density functional theory calculations and the spectroscopic results confirm that the sensing mechanism is photo-induced electron transfer.

Understanding the structure and properties of MgCl2/TiCl4/ID nanoclusters is a key to uncover the origin of Ziegler-Natta catalysis. In this work MgCl2/TiCl4 nanoplatelets derived by machine learning and DFT calculations have been used to model the interaction with ethyl-benzoate EB (as internal donor) with available exposed sites of binary TixCly/MgCl2 systems. The influence of vicinal Ti2Cl8 and coadsorbed TiCl4 on energetic, structural and spectroscopic behaviour of EB has been considered. The adsorption of homogeneous-like TiCl4EB and TiCl4(EB)2 at the various surface sites have been also simulated. Calculations have been carried out by employing B3LYP-D2 and M06 functionals. The adducts have been characterized by computing IR and Raman spectra that have been found to provide specific fingerprints useful to identify surface species; IR spectra have been successfully compared to available experimental data.

: We evaluated the pharmaceutical properties of levofloxacin (LV) in the form of an orally disintegrating tablet (LVODT) to find a new usefulness of low frequency (LF) Raman spectroscopy. LVODT contained dispersed granules with diameters in the order of several hundred micrometers, which were composed of the active pharmaceutical ingredient (API), as confirmed by infrared (IR) microspectroscopy. On the contrary, the API and inactive pharmaceutical ingredients (non-APIs) were homogeneously distributed in LV tablet (LVT) formulations. Microscopic IR spectroscopy and thermal analyses showed that LVODT and LVT contained the API in different crystalline forms or environment around the API each other. Furthermore, powder X-ray diffraction showed that LVT contained a hemihydrate of the API, while LVODT showed a partial transition to the monohydrate form. This result was confirmed by microscopic LF Raman spectroscopy. Moreover, this method confirmed the presence of thin layers coating the outer edges of the granules that contained the API. Spectra obtained from these thin layers indicated the presence of titanium dioxide, suggesting that the layers coexisted with a polymer that masks the bitterness of API. The microscopic LF Raman spectroscopy results in this study indicated new applications of this method in pharmaceutical science.

We introduce a magnetic bead-based sample preparation scheme for enabling a Raman spectroscopic differentiation of severe acute respiratory syndrome coronavirus type 2 (SARS-CoV-2) positive and negative samples. The beads were functionalized with the angiotensin-converting enzyme 2 (ACE2) receptor protein, which is used as recognition element to selectively enrich SARS-CoV-2 on the surface of the magnetic beads. Subsequent Raman measurements directly enable discriminating SARS-CoV-2 positive and negative samples. The proposed approach is applicable for other virus species, too, when the specific recognition element is exchanged. Series of Raman spectra were measured on three types of samples, namely SARS-CoV-2, Influenza A H1N1 virus and a negative control. For each sample type, eight independent replicates were considered. All spectra are dominated by the magnetic bead substrate and no obvious differences between sample types are apparent. In order to address the subtle differences in the spectra, we calculated different correlation coefficients, namely the Pearson coefficient and the Normalized Cross Correlation coefficient. By comparing the correlation with the negative control differentiating between SARS-CoV-2 and Influenza A virus is possible. This study provides a first step towards the detection and potential classification of different viruses with the use of conventional Raman spectroscopy.

Understanding the chalk-fluid interactions and the associated mineralogical and mechanical alteration at sub-micron scale are major goals in Enhanced Oil Recovery. Mechanical strength, porosity, and permeability of chalk are linked to mineral dissolution that occurs during brine injections, and affect the reservoir potential. This paper presents a novel "single grain" methodology to recognize the varieties of carbonates in rocks and loose sediments: Raman spectroscopy is a non-destructive, quick, and user-friendly technique representing a powerful tool to identify minerals down to 1 µm. An innovative working technique for oil exploration is proposed, as the mineralogy of micron-sized crystals grown in two flooded chalk samples (Liége, Belgium) was successfully investigated by Raman spectroscopy. The drilled chalk cores were flooded with MgCl₂ for c. 1.5 (Long Term Test) and 3 years (Ultra Long Term Test) under North Sea reservoir conditions (Long Term Test: 130°C, 1 PV/day, 9.3 MPa effective stress; Ultra Long Term Test: 130°C, varying between 1-3 PV/day, 10.4 MPa effective stress). Raman spectroscopy was able to identify the presence of recrystallized magnesite along the core of the Long Term Test up to 4 cm from the injection surface, down to the crystal size of 1-2 µm. In the Ultra Long Term Test core the growth of MgCO₃ affected nearly the entire core (7 cm). In both samples, no dolomite or high-magnesium calcite secondary growth could be detected when analysing 557 and 90 Raman spectra on the Long and Ultra Long Term Test, respectively. This study can offer Raman spectroscopy as a breakthrough tool in petroleum exploration of unconventional reservoirs, due to its quickness, spatial resolution, and non-destructive acquisition of data. These characteristics would encourage its use coupled with electron microscopes and energy dispersive systems or even electron microprobe studies.

We propose a method for creating parallel Bessel-like vortical optical needles with an arbitrary axial intensity distribution via superposition of different cone-angle Bessel vortices. We analyze the interplay between the separation of individual optical vortical needles and their respective lengths and introduce a super-Gaussian function as their axial profile. We also analyze the physical limitations to observe well-separated optic needles, as they are influenced by mutual interference of the individual beams. To verify our theoretical and numerical results, we generate controllable spatial arrays of individual Bessel beams with various numbers and spatial separations by altering the spectrum of the incoming laser beam via the spatial light modulator. We demonstrate experimentally how to implement such beams using a diffractive mask. The presented method facilitates the creation of diverse spatial intensity distributions in three dimensions, potentially finding applications in specific microfabrication tasks or other contexts. These beams may have benefits in laser material processing applications such as nanochannel machining, glass via production, modification of glass refractive indices, and glass dicing.

Experimental studies on the development of processes of obtaining ultradispersed metal-ceramic materials and coatings Mo-ZrO₂, Mo-Al₂O₃, W-ZrO₂, W-Al₂O₃ CVD by deposition from the gas phase in CO₂ process using low-temperature nonequilibrium plasma were carried out.The structure, microhardness, phase composition, and high-temperature annealing behavior of the materials were studied. It is shown that the choice of parameters of the deposition process and temperature annealing can be controlled by the distribution function of ultradispersed particles in the material and their sizes.High-temperature X-ray studies of "molecular" two-phase alloys Mo- Al₂O₃ and Mo- ZrO₂show that, depending on the elastic and thermal properties of the matrix materials and dispersed particles, the molybdenum matrix can be in an all-round tensed or all-round compressed state.In the study of the electro-physical characteristics of the two-phase disperse-strengthened alloys Mo- ZrO₂, Mo- Al₂O₃, W- ZrO₂, W- Al₂O₃ it has been established that in the region of temperatures 1023...1273K anomalous changes of specific electrical resistance and instability of thermal eddy in magnitude are observed apparently connected with the presence of internal stresses in material caused by ultradisperse particles.Theoretical aspects of the problem of increasing the carriers density in nanocomposite materials are reviewedTheoretical analysis of the effect of the ensemble of microparticles on the change of electron density in ultradisperse metal-ceramic materials is carried out. It is shown that the average values of the electron density in the matrix with the introduction of 1% of particles with a radius of 50 A increase by more than two orders of magnitude.The possibilities of creating ultradisperse compositions using radiation-plasma methods are considered.

Diseases in articular cartilages have affected millions of people globally. Although the biochemical and cellular composition of articular cartilages is relatively simple, there is the limitation in self-repair ability of cartilage. Therefore, developing the strategies for cartilage repair is very important. Here, we reported a new manufacturing process of water-based polyurethane based photosensitive materials with hyaluronic acid and applied the materials for 3D printed customized cartilage scaffolds. The scaffold has high cytocompatibility and is one that closely mimics the mechanical properties of articular cartilages. It is suitable for culturing human Wharton's jelly mesenchymal stem cells (hWJMSCs) and the cells showed an excellent chondrogenic differentiation capacity. We consider that the 3D printing hybrid scaffolds may have potential in customized tissue engineering and facilitate the development of cartilage tissue engineering.

In this paper we present magnetoelectric properties of metal/metal-oxide/metal junctions. We use Ti and Fe as metallic layers separated by the porous metal-oxides of iron or titanium formed with the anodization method. This allowed to prepare double junctions with at least one ferromagnetic layer. Here we show magnetoresistance and current-voltage characteristics of the junctions together with their magnetic characteristics. We found positive or negative magnetoresistance depending on junction composition. We discuss also the nature of differential resistance calculated from I-V characteristics. Our findings show that the strongest influence on observed behaviour has a top metallic layer and the interface between this layer and anodized oxide where strong interatomic diffusion is expected.

Micro-Raman spectroscopy was carried out to evaluate the localized residual stresses in commercial Gallium Nitride-based devices, specifically AlGaN/GaN High Electron Mobility Transistors (HEMTs) in a novel packaging design provided by STMicroelectronics S.r.l. The packaging plays a key role in protecting the device core against the external environment, thus minimizing damages caused by mechanical shocks, exposure to light, and contact with chemicals, conjointly achieving an efficient heat dissipation rate. Even though the packaging is a required step for the proper functioning of ready-to-use electronic devices, its application typically may introduce mechanical stress to AlGaN/GaN HEMTs, which can result in various reliability issues. In this paper, we investigate the impact of packaging on residual stress by analyzing the frequency shift of the E2 Raman peak along GaN layers and at the GaN/Si interface. An extensive evaluation was conducted using both a packaged device and a wafer-level device. The correlation between Raman frequency shifts of the E2 mode was accurately quantified, revealing a stress mitigation of approximately 0.1 GPa. This reduction is ascribed to the compressive stress introduced by the packaging, which partially offsets the intrinsic tensile stress of the wafer-level device. The proposed methodology could, in principle, be implemented to improve the development of a packaging.

The enzyme-linked immunosorbent assay (ELISA) coupled with surface-enhanced Raman spectroscopy (SERS) detection is a growing area of analytical chemistry emerged as a solution to a problem of sensitivity improvement. SERS-based ELISA with horseradish peroxidase as an enzymatic label, o-phenylenediamine (oPD) substrate, and 2,3-diaminophenazine (DAP) enzymatic product was one of the first examples of such systems. Surprisingly, the full potential of this long-known approach has not been revealed yet. The current study addresses a previously neglected problem of SERS detection stage performance. Using silver nanoparticles and model mixtures of oPD and DAP, the effects of pH, concentration of aggregating agent, and particle surface chloride stabilizer were extensively evaluated. At optimal mildly acidic pH of 3, 0.93 to 1 M citrate buffer, and AgNPs stabilized with 20 mM chloride, at least two orders of magnitude advantages in the detection limits of SERS over colorimetry both for DAP and HRP were demonstrated. We suppose that this improved detection system could become a useful tool for the development of SERS-based ELISA protocols.

This work describes a resonance Raman study performed in domes of monolayer MoS2 using 23 different laser excitation energies covering the visible and near-infrared (NIR) ranges. The multiple-excitation results allowed us to investigate the exciton-phonon interactions of different phonons (A1’, E’ and LA) with different electronic and excitonic optical transitions in biaxially strained monolayer MoS2. The analysis of the intensities of the two first-order peaks, A1’ and E’, and the double-resonance 2LA Raman band as a function of the laser excitation furnished the values of the energies of the indirect gap and the excitonic transitions in the strained MoS2 domes. It was noticed that the out-of-plane A1’ phonon mode is significantly enhanced only by the indirect gap I and the C exciton, whereas the in-plane E’ mode is only enhanced by the C exciton of MoS2 dome, revealing thus a weak interaction of these phonons with the A and B excitons in the strained MoS2 domes. On the other hand, the 2LA Raman band is significantly enhanced at the indirect gap I transition and by the A (or B) exciton, but not enhanced by the C exciton, showing thus that the LA edge-phonons that participate in the double resonance process in MoS2 have a weak interaction with the C exciton.

The combination of eco-respectful epoxy compounds with the humins, a by-product of biomass chemical conversion technologies, allow the obtention of materials with high added value. In this work, we propose the chemical connection study of humins with two aliphatic diepoxides through the copolymerization reactions to synthesize sustainable bio-based thermosets. The mechanism insights for the crosslinking between the epoxides and humins was proposed considering the different functionalities of the humins structure. FT-IR spectroscopy, 1 D and 2 D NMR spectroscopy techniques were used to build the proposed mechanism. By these techniques, the principal chain connections and the reactivity of all the components were highlighted in the synthesized networks.

Metal complexes of mesoionic carbenes (MICs) of the triazolylidene-type and their derivatives have gained increasing attention in the fields of electrocatalysis and photochemistry. The redox-activity of these metal complexes is critical for their applications in both the aforementioned fields. Easy accessibility and modular synthesis open a wide field for the design of ligands, such as bidentate ligands. The combination of a MIC with a pyridyl unit in a bidentate ligand setup increases the π-acceptor properties of the ligands while retaining their strong σ-donor properties. The analogy with the well-established 2,2'-bipyridine ligand allows conclusions to be drawn about the influence of the mesoionic carbene (MIC) moiety in tetracarbonyl group 6 complexes in cyclic voltammetry and (spectro-)electrochemistry (SEC). However, the effects of the different connectivity in pyridyl-MIC ligands remains underexplored. Based on our previous studies, we present here a thorough investigation of the influence of the two different pyridyl-MIC constitutional isomers on the electrochemical and the UV-vis-NIR/IR/EPR spectroelectrochemical properties of group 6 carbonyl complexes. Moreover, the presented complexes were investigated for the electrochemical conversion of CO2 using two different working electrodes, providing a fundamental understanding of the influence of the electrode material in the precatalytic activation.

The industry of the counterfeit goods is one of the largest underground business in the world and it is rapidly growing. Counterfeits can lead not only to loss of profit for honest producers but also have a negative impact on consumers who receive poor quality goods at an excessive price and may be exposed to health damages and safety issues. Perfume industry is constantly exposed to the problem of counterfeits with the fast developing parallel market of inspired perfumes being an important issue. It prompts for the identification of methods that classify the quality of this type of products. In this paper the application of proton nuclear magnetic resonance spectroscopy is employed for the authentication of perfumery products for the first time. Molecular composition of several types of authentic brand fragrances for women were compared with their cheaper inspired equivalents and fake products. Our approach offers the prospect of a fast and simple method for discrimination and counterfeit detection of perfumes using 1H NMR spectroscopy.

The food additive sorbic acid is considered as an effective preservative for certain cereal products, and propionic acid is commonly added in bakery wares, e.g. bread and fine bakery wares. The aim of this study is to develop and validate a new nuclear magnetic resonance spectroscopy (¹H NMR) method for routine screening and quantification of sorbic and propionic acids in bread and several bakery products for quality control purposes. Results showed that none of the screened samples contained higher concentrations than regulatory maximum limits. However, for some samples, labelling of preservatives was lacking or they were used in food categories, for which the use is not approved. It can be concluded that the developed NMR method can be used for routine screening of bakery products.

The poly lactic acid (PLA) is one of the most used bio-derived thermoplastic polymers in 3D and 4D printing applications. The determination of PLA surface properties is of capital importance in 3D/4D printing technology. (1) Background: The surface thermodynamic properties of PLA polymer were determined by using the inverse gas chromatography (IGC) technique at infinite dilution. The determination of the retention volume of polar and non-polar molecules adsorbed on the PLA particles filling the column allowed us to obtain the dispersive, polar, and Lewis’s acid-base surface properties at different temperatures from 40 °C to 100 °C. (2) Methods: the applied surface method was based on our recent model that used the London dispersion equation and the new chromatographic parameter function of the deformation polarizability and the harmonic mean of the ionization energies of the PLA polymer and organic molecules. (3) Results: The application of this new method led to the determination of the dispersive and polar free surface energy of adsorption of molecules on the polymeric material, as well as the glass transition and the Lewis acid-base constants. (4) Conclusions: four interval temperatures were distinguished showing four zones of the variations of the surface properties of PLA as a function of the temperature before and after the glass transition.

Fibromyalgia (FM) is a chronic central sensitivity syndrome characterized by augmented pain processing at diffuse body sites and presents as a multimorbid clinical condition. Long COVID (LC) is a heterogenous clinical syndrome that affects 10-20% of individuals following COVID-19 infection. FM and LC shares similarities with regards to the pain and other clinical symptoms experienced, thereby posing a challenge for accurate diagnosis. This research explores the feasibility of using surface enhanced Raman spectroscopy (SERS) combined with soft independent modelling of class analogies (SIMCA) to develop classification models differentiating LC and FM. Venous blood samples were collected using two supports, dried bloodspot cards (DBS, n= 48 FM and n= 46 LC) and volumetric absorptive micro sampling tips (VAMS, n= 39 FM and n= 39 LC). A semi-permeable membrane (10 kDa) was used to extract low molecular fraction (LMF) from the blood samples, and Raman spectra was acquired using SERS with gold nanoparticles (AuNPs). Soft Independent Modelling of Class Analogy (SIMCA) models developed with spectral data of blood samples collected in VAMS tips showed superior performance with a validation performance of 100% accuracy, sensitivity, and specificity achieving an excellent classification accuracy of 0.86 area under the curve (AUC). Amide groups, aromatic and acidic amino acids were responsible for the discrimination patterns among FM and LC syndromes, emphasizing the findings from our previous studies. Overall, our results demonstrate the ability of AuNPs SERS to identify unique metabolites that can be potentially used as spectral biomarkers to differentiate FM and LC.

Raman Spectroscopy has long been anticipated to augment clinical decision making, such as classifying oncological samples. Unfortunately, the complexity of Raman data has thus far inhibited its routine use in clinical settings. Traditional machine learning models have been used to help exploit this information, but recent advances in deep learning have the potential to improve the field. However, there are a number of potential pitfalls with both traditional and deep learning models. We conduct a literature review to ascertain the recent machine learning methods used to classify cancers using Raman spectral data. We find that while deep learning models are popular, and ostensibly outperform traditional learning models, there are many methodological considerations which may be leading to an over-estimation of performance: primarily, small sample sizes which compound upon sub-optimal choices regarding sampling and validation strategies. Amongst several recommendations is a call to collate large benchmark Raman datasets, similar to those that have helped transform digital pathology, which researchers can use to develop and refine deep learning models.

The conformational preferences of the ester group have the potential to facilitate the large amplitude folding of long alkyl chains in the gas phase. They are monitored by Raman spectroscopy in supersonic jet expansions for the model system methyl butanoate, after establishing a quantitative relationship to quantum-chemical predictions for methyl methanoate. This requires a careful analysis of experimental details, and a simulation of the rovibrational contours for near-symmetric top molecules. The technique is shown to be complementary to microwave spectroscopy in quantifying coexisting conformations. It confirms that a C-O-C(=O)-C-C chain segment can be collapsed into a single all-trans conformation by collisional cooling, whereas alkyl chain isomerism beyond this five-membered chain largely survives the jet expansion. This sets the stage for the investigation of linear alkyl alkanoates in terms of dispersion-induced stretched-chain to hairpin transitions by Raman spectroscopy.

Background: Hyaluronic acid (HA) is well known in the cosmetic industry for its hydrating properties linked to its interaction with keratin in the stratum corneum. Hair is also mainly composed of keratin, but no evidence of penetration and interaction of HA in hair had yet been established. Herein, we examined, with appropriate methods, this penetration and interaction. Methods: Confocal Raman Spectroscopy was used to track HA penetration in hair fibers. Human hair was UV-irradiated, or not, before washing with a number of different shampoo formulations. Low-molecular weight hyaluronic acid, high-molecular weight HA, and an optimized blend of low- and high-molecular weight HA, were used. The benefits of HA for cosmetic application were then evaluated at the ex vivo level. Results: Raman analysis of non-irradiated samples revealed that the HA blend penetrated the hair cortex 5.9 times more than the placebo and with irradiated samples, a 1.8-fold increase in penetration was observed. Whatever the irradiation status, penetration of this optimal HA blend was significantly greater than that of the other two active substances. Compared to the placebo, the HA blend significantly decreased spontaneous frizzing by 11%, repaired the hair by increasing the elastic modulus and the break force, and increased the water content in the hair shafts. Conclusion: Confocal Raman Spectroscopy can be considered as a powerful, non-invasive technique to investigate the penetration of active ingredients into the hair.

In aqueous solution planar bis(1,2-dithiooxalato)nickelates(II), [Ni(dto)2]2- react with lanthanide ions (Ln3+) to form pentanuclear, hetero-bimetallic complexes of the general composition [{Ln(H2O)n}2{Ni(dto)2}3] · x H2O (n = 4 or 5; x = 9 - 12). Two complexes of this series, [{Pr(H2O)5}2{Ni(dto)2}3] · 11 H2O, Pr2Ni3 1 and [{Gd(H2O)5}2{Ni(dto)2}3] · 11 H2O, Gd2Ni3 2 were synthesized and characterized by single crystal X-ray structure analysis, X-ray powder diffraction, and IR spectroscopy. All Ln2Ni3 complexes crystallize as monoclinic crystals in the space group P21/c.

This article proposes the use of a multi-scale and multi-sensor approach to collect and modelling 3D data concerning wide and complex areas in order to obtain a variety of metric information in the same 3D archive, based on a single coordinate system. The employment of these 3D georeferenced products is multifaceted and the fusion or integration among different sensors data, scales and resolutions is promising and could be useful for the generation of a model that could be defined as hybrid. The correct geometry, accuracy, radiometry and weight of the data models are hereby evaluated comparing integrated processes and results from Terrestrial Laser Scanner (TLS), Mobile Mapping System (MMS), Unmanned Aerial Vehicle (UAV), terrestrial photogrammetry, using Total Station (TS) and Global Navigation Satellite System (GNSS) as topographic survey. The entire analysis underlines the potentiality of the integration and fusion of different solutions and is a crucial part of the “Torino 1911” project whose main purpose is mapping and virtually reconstructing the 1911 Great Exhibition settled in the Valentino Park in Turin (Italy).

A portable laser photoacoustic sensor based on a Field-Programmable Gate Array (FPGA) is reported for methane detection. A tunable DFB diode laser in the 1654 nm wavelength range is used as an excitation source. The photoacoustic signal processing was implemented by a FPGA device. A small resonant photoacoustic cell is designed. The minimum detection limit (1σ) of 10 ppm for methane (CH₄) is demonstrated.

Microwave technology has a potential application in the extraction of zinc from sulphide ores, knowledge of the dielectric properties of these ores plays a major role in the microwave design and simulation for any process. The dielectric properties of zinc sulfide concentrate for two different apparent densities—1.54 and 1.63 g/cm³—have been measured by using the resonance cavity perturbation technique at 915 and 2450 MHz during the roasting process for the temperature ranging from room temperature to 850 °C. The variations of dielectric constant, the dielectric loss factor, the dielectric loss tangent and the penetration depth with the temperature, frequency and apparent density have been investigated numerically. The results indicate that the dielectric constant increases as the temperature increases and temperature has a pivotal effect on the dielectric constant, while the dielectric loss factor has a complicated change and all of the temperature, frequency and apparent density have a significant impact to dielectric loss factor. Zinc sulfide concentrate is high loss material from 450 to 800 °C on the basis of theoretical analyses of dielectric loss tangent and penetration depth, its ability of absorbing microwave energy would be enhanced by increasing the apparent density as well. The experimental results also have proved that zinc sulfide concentrate is easy to be heated by microwave energy from 450 to 800 °C. In addition, the experimental date of dielectric constant and loss factor can be fitted perfectly by Boltzmann model and Gauss model, respectively.

Germanium is an essential microelement, and its deficiency can result in numerous diseases, particularly oncogenic conditions. Consequently, water-soluble germanium compounds, including inorganic and coordination compounds, have attracted significant attention due to their biological activity. The review analyzes the primary research from the last decade related to the anticancer activity of germanium compounds. Furthermore, the review clarifies their actual toxicity, identifies errors and misconceptions that have contributed to the discrediting of their biological activity, and suggests a putative mechanism of germanium-mediated protection from oxidative stress. Finally, the review provides clarifications on the discovery history of water-soluble organic germanium compounds, which was distorted and hushed up for a long time.

The ability of 2D hybrid structures formed by boron, nitrogen and carbon atoms (h-BNCs) as potential substrates for surface enhanced Raman spectroscopy (SERS) detection of dioxin-like pollutants is theoretically analyzed. The strong confinement and high tunability of the electromagnetic response of the carbon nanostructures embedded within the h-BNC sheets point out that these hybrid structures could be promising for applications in optical spectroscopies, such as SERS. In this work, two model dioxin-like pollutants, TCDD and TCDF, and a model h-BNC surface composed by a carbon nanodisk of ninety-six atoms surrounded by a string of borazine rings, BNC96, are employed for the simulation of the adsorption complexes and the static and pre-resonance Raman spectra of the adsorbed molecules. A large affinity of BNC96 by these pollutants is reflected on the large interaction energies obtained for the most stable stacking complexes, with dispersion being the most important contribution to their stability. The large vibrational coupling of some active modes of TCDF and, specially, of TCDD makes the Raman static spectra display a ‘pure’ chemical enhancement of one order of magnitude. On the other hand, due to the strong electromagnetic response of BNC96, confined within the carbon nanodisk, pre-resonance Raman spectra obtained for TCDD and TCDF display large enhancement factors of 108 and 107, respectively. Promisingly, laser excitation wavelengths frequently used in SERS experiments also provoke significant Raman enhancements, around 104, for the TCDD and TCDF signals. Both the strong confinement of the electromagnetic response within the carbon domains and the high modulation of the resonance wavelengths within the visible and/or UV ranges in h-BNCs should lead to a higher sensitivity than graphene and white graphene parent structures, solving one of the main disadvantages of using 2D substrates for SERS applications.

Dimers and oligomers of alkenes represent a category of compounds that are in great demand for diverse industrial sectors. Among the developing synthetic methods, the catalysis of alkene dimerization and oligomerization using transition metal salts and complexes is of undoubted interest for practical application. This approach demonstrates substantial potential, offering not only elevated reaction rates but also precise control over the chemo-, regio-, and stereoselectivity of the reactions. In this review, we discuss the data on catalytic systems for alkene dimerization and oligomerization. Our focus lies in the analysis of how the activity and chemoselectivity of these catalytic systems are influenced by various factors, such as the nature of the transition metal, the ligand environment, the activator, and substrate structure. Notably, the review particularly discusses the reaction mechanisms, encompassing metal complex activation, structural and dynamic features, and the reactivity of hydride intermediates, which serve as potential catalytically active centers in alkene dimerization and oligomerization.

The biological synthesis of nanoparticles has been emerging as an environmentally benign and eco-friendly method owing to its cost-effectiveness and high efficiency. Recently, the biological synthesis of semiconductor and metal-doped semiconductor nanoparticles with enhanced photocatalytic degradation efficiency and anticancer and antibacterial properties have gained tremendous attention. In pursuit of this purpose, for the first time, we biosynthesized zinc oxide (ZnO) and silver/ZnO nanocomposites (NCs) as semiconductor and metal-doped semiconductor nanoparticles, respectively, using the cell-free filtrate (CFF) of Lysinibacillus sphaericus bacterium. The biosynthesized ZnO and Ag/ZnO were characterized by various techniques such as ultraviolet-visible spectroscopy, X-ray diffraction, Fourier-transform Infrared spectroscopy, Field-emission scanning electron microscopy, transmission electron microscopy, and photoluminescence spectroscopy. The photocatalytic degradation potential of these semiconductor/metal-semiconductor nanoparticles was evaluated against the degradation of azo dye methylene blue (MB) under simulated solar irradiation. Ag/ZnO showed 90.7 ± 0.91% photocatalytic degradation of MB, compared to 50.7 ± 0.53% by ZnO in 120 min. The cytotoxicity of ZnO and Ag/ZnO on human cervical HeLa cancer cells was determined using an MTT assay. Both nanomaterials exhibited cytotoxicity in a concentration-dependent and time-dependent manner on HeLa cells. The antibacterial activity was also determined against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus). Compared to ZnO, Ag/ZnO NPs showed higher antibacterial activity. Hence, the biosynthesis of semiconductor nanoparticles could be a promising strategy for developing hybrid metal/semiconductor nanomaterials for different biomedical and environmental applications.

Porphyrinic photosensitizers (PSs) and their nano-sized polymer-based carrier systems are required to exhibit low dark toxicity, avoid side effects, and ensure high in vivo tolerability. Yet, little is known about the intracellular fate of PSs during the dark incubation period and how it is af-fected by nanoparticles. In a systematic study, high resolution magic angle spinning NMR spectroscopy combined with statistical analyses was used to study the metabolic profile of cultured HeLa cells treated with different concentrations of the PS chlorin e4 (Ce4) alone or encapsulated in carrier systems. For the latter, either polyvinylpyrrolidone (PVP) or the micelle forming polyethylene glycol (PEG)-polypropylene glycol triblock copolymer Kolliphor P188 (KP) were used. Diffusion edited spectra indicated Ce4 membrane localization evidenced by Ce4 concentration dependent chemical shift perturbation of the cellular phospholipid choline resonance. The effect was also visible in the presence of KP and PVP, but less pronounced. The appearance of the PEG resonance in the cell spectra pointed towards cell internalization of KP whereas no conclusion could be drawn for PVP that remained NMR-invisible. Multivariate statistical analyses of the cell spectra (PCA, PLS-DA and oPLS) revealed a concentration-dependent metabolic response upon exposure to Ce4 that was attenuated by KP and even more by PVP. Significant Ce4-concentration dependent alterations were mainly found for metabolites involved in the tricarboxylic acid cycle and the phosphatidylcholine metabolism. The data underline an important protective role of the polymeric carriers following cell internalization. Moreover, the current study allowed - to our knowledge for the first time - to trace the intracellular PS localization on an atomic level by NMR methods.

Abstract: Beetroot (Beta vulgaris L) has been known for being a rich source of phytochemicals, minerals and vitamins. This study presents a model system for how the combination of extrac-tion/chromatography/mass spectrometry and NMR offers an efficient way to profile metabolites in the extracts of a natural product, beetroot . Such combination may lead to the identification of more nutritional or medicinal compounds in natural products, and it is essential for our ongoing investigation to study the selective adsorption/desorption of these metabolites on nanoparticles. The aqueous and organic extracts underwent analyses using UV-vis spectroscopy; GC-MS; LC-MS; 1H, 13C, TOCSY, HSQC, and selective TOCSY NMR experiments. Polar Extract: The two forms of betalain pigment were identified by UV-vis and LC MS. Fourteen amino acids, sucrose, and other compounds among which is riboflavin, were identified by LC-MS. 2D TOCSY showed the spin coupling correlations corresponding to some of these compounds. The HSQC spectrum showed 1H/13C spin correlation in sucrose confirming the high abundance of sucrose in beetroot. Organic Extract: GC-MS data enabled the identification of several compounds including six fatty acid methyl esters (FAME) with higher than, on average, 90% similarity score. Selective TOCSY NMR data showed the spin coupling pattern corresponding to oleic, linoleic, and linolenic fatty acids. 31P NMR spectra indicate that phospholipids exist in both the organic and aqueous phases. Keywords: Beetroot (Beta vulgaris L); Total Correlation Spectroscopy (TOCSY); Gas Chromatog-raphy-Mass Spectrometry (GC-MS); selective TOCSY, Homonuclear single quantum correlation (HSQC); fatty acid methyl esters (FAME).

The article is devoted to the topical problem of estimating water content in water-oil mixtures and porous media they saturate, according to low-field NMR relaxometry and dielectric spectroscopy. The aim of the research is to theoretically substantiate and experimentally validate the capability of joint interpretation of data from these methods to acquire information on the filtration-volumetric properties of drill cuttings, relaxation characteristics of oil-containing fluids, water/oil ratio in water-oil mixtures and saturated with them drill cuttings in order to control the composition of liquids produced from boreholes. The studies were carried out on samples of cuttings and oils taken from fields in the northern and Arctic regions of the West Siberian oil-and-gas province. Based on the experimental data obtained, we evaluated the water content in the water-oil mixtures, determined the main NMR parameters of the mixtures in terms of properties of the constituent oils, and specified the parameters and shapes of NMR and complex dielectric permittivity spectra. The NMR method was found to be effective in examining high-viscosity and medium-viscosity oils, while the dielectric spectroscopy method – in the study of light oils; their integration allows obtaining reliable data for all the samples under study. We also showed how the shapes of NMR and complex dielectric permittivity spectra depend on the rheological properties of oil belonging to the mixture.

Optical remote sensing can contribute to biodiversity monitoring and species composition mapping in tropical forests. Inferring ecological information from canopy reflectance is complex and data availability suitable to such a task is limiting, which makes simulation tools particularly important in this context. We explored the capability of the 3D radiative transfer model DART to simulate top of canopy reflectance acquired with airborne imaging spectroscopy in complex tropical forest, and to reproduce spectral dissimilarity within and among species, as well as species discrimination based on spectral information. We focused on two factors contributing to these canopy reflectance properties: the horizontal variability in leaf optical properties (LOP) and the fraction of non-photosynthetic vegetation (NPVf). The variability in LOP was induced by changes in leaf pigment content, and defined for each pixel based on a hybrid approach combining radiative transfer modeling and spectral indices. The influence of LOP variability on simulated reflectance was tested by considering variability at species, individual tree crown and pixel level. We incorporated NPVf into simulations following two approaches, either considering NPVf as a part of wood area density in each voxel or using leaf brown pigments. We validated the different scenarios by comparing simulated scenes with experimental airborne imaging spectroscopy using statistical metrics, spectral dissimilarity (within crowns, within species, and among species dissimilarity) and supervised classification for species discrimination. The simulation of NPVf based on leaf brown pigments resulted in the closest match between measured and simulated canopy reflectance. The definition of LOP at pixel level resulted in conservation of the spectral dissimilarity and expected performances for species discrimination. Our simulation framework could contribute to better understand performances for species discrimination and relationship between spectral variations and taxonomic and functional dimensions of biodiversity.

Development of novel anti-cancer peptides requires a rapid screening process which can be accelerated by using appropriate in vitro tumor models. Breast carcinoma tissue is a three dimensional (3D) microenvironment, which contains a hypoxic center surrounded by dense proliferative tissue. Biochemical clues provided by such 3D cell mass cannot be recapitulated in conventional 2D culture systems. In this experiment, we evaluate the efficacy of the sandalwood peptide, cyclosaplin on established in vitro 3D silk breast cancer model using invasive MDA-MB-231 cell line. The anti-proliferative effect of the peptide on 3D silk tumor model is monitored by alamar blue assay, with conventional 2D culture as control. The proliferation rate, glucose consumed, LDH, and MMP-9 activity of Human breast cancer cells are higher in 3D constructs compared to 2D. A higher concentration of drug is required to achieve 50% cell death in 3D culture than 2D cultures. The cyclosaplin treated MDA-MB-231 cells showed significant decrease in MMP-9 activity in 3D constructs. Microscopic analysis revealed the formation of cell clusters evenly distributed in the scaffolds. The drug treated cells were less in number, smaller and showed unusual morphology. Overall, these findings indicate the role of cyclosaplin as a promising anti-cancer therapeutics.

The interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC) has been extensively utilized to synthesize nanofiltration (NF) membranes. However, it is still a huge challenge to monitor the IP reaction, because of the fast reaction rate and the formed ultra-thin film. Herein, two effective strategies were applied to reduce the IP reaction rate: (1) the introduction of hydrophilic interlayers between the porous substrate and the formed polyamide layer, and (2) the addition of macromolecular additives in the aqueous solution of PIP. As a result, in situ Fourier transform infrared (FT-IR) spectroscopy was firstly used to monitor the IP reaction of PIP/TMC with hydrophilic interlayers or macromolecular additives in the aqueous solution of PIP. Moreover, the formed polyamide layer growth on the substrate was studied in a real-time manner. The in situ FTIR experimental results confirmed that the IP reaction rates were effectively suppressed and that the formed polyamide thickness was reduced from 138 ± 24 nm to 46 ± 2 nm according to TEM observation. Furthermore, an optimized NF membrane with excellent performance was consequently obtained, which included boosted water permeation of about 141–238 (L/m²·h·MPa) and superior salt rejection of Na₂SO₄ > 98.4%.

The thionamide antithyroid drugs were discovered largely following serendipitous observations by numerous researchers in the 1940s who found that sulfhydryl-containing compounds were goitrogenic in animals. Prof. Edwin B. Astwood was the first to use these compounds to treat hyperthyroidism. In this review, we summarize the history of the development of these drugs and the coordination possibility of 2-thiouracil and its derivatives, as well as the biological activities of some of its complexes. Some of them are used as agents for the treatment of tuberculosis, and arthritis, others have bactericidal and fungicidal activity, the third cytotoxic properties, and could be used to treat various types of cancer.

Novel sensing technologies for liquid biopsies offer a promising prospect for the early detection of metabolic conditions through -omics techniques. Indeed, high-field NMR facilities are routinely used for metabolomics investigations on a range of biofluids in order to rapidly recognize unusual metabolic patterns in patients suffering from a range of diseases. However, these techniques are restricted by the prohibitively large size and cost of such facilities, suggesting a possible role for smaller, low-field NMR instruments in biofluid analysis. Herein we describe selected biomolecule validation on a low-field benchtop NMR spectrometer (60 MHz), and present an associated protocol for the analysis of biofluids on compact NMR instruments. We successfully detect common markers of diabetic control at low-to-medium concentrations through optimized experiments, including glucose (≤ 2.6 mmol./L) and acetone (25 μmol./L), and additionally in readily-accessible biofluids. We present a combined protocol for the analysis of these biofluids with low-field NMR spectrometers for metabolomics, and offer a perspective on the future of this technique appealing to point-of-care applications.

The radar sensor described realizes healthcare monitoring capable of detecting subject chest-wall movement caused by cardiopulmonary activities, and wirelessly estimating the respiration and heartbeat rates of the subject without attaching any devices to the body. Conventional single-tone Doppler radar can only capture Doppler signatures because of a lack of bandwidth information with noncontact sensors. In contrast, we take full advantage of impulse radio ultra-wideband (IR-UWB) radar to achieve low power consumption and convenient portability, with a flexible detection range and desirable accuracy. A noise reduction method based on improved ensemble empirical mode decomposition (EEMD) and a vital sign separation method based on the continuous-wavelet transform (CWT) are proposed jointly to improve the signal-to-noise ratio (SNR) in order to acquire accurate respiration and heartbeat rates. Experimental results illustrate that respiration and heartbeat signals can be extracted accurately under different conditions. This noncontact healthcare sensor system proves the commercial feasibility and considerable accessibility of using compact IR-UWB radar for emerging biomedical applications.

Artic root is a well-known plant adaptogen with multipotential pharmacological properties. Thin-layer chromatography (TLC) – screening followed by diode-array high-performance liquid chromatography and nuclear magnetic resonance spectroscopy proved to be a reliable and convenient method for simultaneous determination of quality of various herbal raw materials and supplements. This combination allowed for comparing and differentiating arctic root samples as well as defining their authenticity. The study provided information on the chemical and biological properties of the seven chosen samples as well as qualitative and quantitative evaluation of the quality markers: rosavin, salidroside, and p-tyrosol. The absence of rosavin, salidroside, and p-tyrosol in three samples was detected using TLC-screening and confirmed by HPLC-DAD and NMR. The paper highlighted the importance of quality control and strict regulation for herbal medicine supplements and preparations.

Laser-induced periodic surface structures (LIPSS) have gained significant attention due to their ability to modify the surface morphology of materials at the micro-nanoscale and show great promise for surface functionalization application. In this study, we specifically investigate the formation of LIPSS in silicon substrates and explore their impact on Surface-Enhanced Raman Spectroscopy (SERS) applications. This study reveals a stepwise progression of LIPSS formation in silicon, involving three distinct stages of LIPSS: 1) integrated Low-Spatial-Frequency LIPSS (LSFL) and High-Spatial-Frequency LIPSS (HSFL), 2) principally LSFL and 3) LSFL at the edge of the irradiated spot, elucidating the complex interplay between laser fluence, pulse number, and resulting surface morphology. Furthermore, from an application standpoint, these high-quality multi-scale periodic patterns lead to the next step of texturing the entire silicon surface with homogeneous LIPSS for SERS application. The potential of LIPSS-fabricated silicon substrates for enhancing SERS performance is investigated using thiophenol as a test molecule. The results indicate that the Au-coated combination of LSFL and HSFL substrate showcased the highest enhancement factor (EF) of 1.38 × 10^6. This pronounced enhancement is attributed to the synergistic effects of Localized Surface Plasmon Resonance (LSPR) and Surface Plasmon Polaritons (SPPs), intricately linked to HSFL and LSFL characteristics. These findings contribute to understanding LIPSS formation in silicon and their applications in surface functionalization and SERS, paving the way for sensing platforms.

Bis-benzimidazole derivative (BBM) molecule, consisting of two 2-(2’-Hydroxyphenyl) benzim-idazole (HBI) halves, has been synthesized and successfully utilized as a ratiometric fluorescence sensor for the sensitive detection of Cu2+ based on enol-keto excited state intramolecular proton transfer (ESIPT). In this study, we strategically implement femtosecond stimulated Raman spec-troscopy and several time-resolved electronic spectroscopies, aided by quantum chemical calcula-tions to investigate the detailed primary photodynamics of BBM molecule. The results demonstrate that the ESIPT from BBM-enol* to BBM-keto* was observed in only one of HBI halves with a time constant of 300 fs, after that, the rotation of the dihedral angle between two HBI halves generate a planarized BBM-keto* isomer in 3 ps, leading to dynamics red shift of BBM-keto* emission.

Scientific evidence increasingly supports the strong link between diet and health, acknowledging that a well-balanced diet plays a crucial role in preventing chronic diseases such as obesity, diabetes, cardiovascular issues, and certain types of cancer. This perspective opens the door to developing precision diets, particularly tailored for individuals at risk of developing cancer. It encompasses a vast research area and involves the study of an expanding array of compounds with multi-level "omics" compositions, including genomics, transcriptomics, proteomics, epigenomics, miRNomics, and metabolomics. We review here the components of the Southern European Atlantic Diet (SEAD) from both a chemical and pharmacological standpoint. The information sources consulted, complemented by crystallographic data from the Protein Data Bank, establish a direct link between SEAD and its anticancer properties. The data collected strongly suggest that SEAD offers an exceptionally healthy profile, particularly due to the presence of beneficial biomolecules in its foods. The inclusion of olive oil and paprika in this diet provides numerous health benefits, and science supports the anti-cancer properties of dietary supplements with biomolecules sourced from vegetables of the brassica genus. Nonetheless, further research is warranted in this field to gain deeper insights into the potential benefits of SEAD's bioactive compounds against cancer.

Pretreatment of cells with proteolysis inhibitors diminished intensity and changed shape of DNICs specific EPR signal in a treatment time-dependent manner. The level of DNIC formation was significantly influenced by the presence of protein degradation products. Interestingly, formation of HMWDNICs depended on the availability of LMWDNICs. The extent of glutathione involvement in the in vivo formation of DNICs is minor yet noticeable, aligning with our prior research findings.

A new Pd(II) complex of the previously reported ligand N,N′-bis[(2,2′-dihydroxybiphen-3-yl)methyl]-N,N′-dimethylethylenediamine (L) was obtained from a DMF/H2O mixture. It differs from a Pd(II) complex of L previously obtained by sole DMF. The roles in the solid state assembly of solvent molecules and molecular conformation (driven by specific transition metal ions) were studied by comparing six complexes of L containing different metal centers (Ni(II), Cd(II), Cu(II), Pd(II)). Hirshfeld surface analysis, 2D fingerprint plots and energy frameworks calculations were used to investigate the intermolecular interactions within the crystal packing of the six complexes. As suggested by interaction energies, Pd(II) and Ni(II) complexes arrange to form ribbons, while Cd(II) and Cu(II) complexes form 3D networks. Interactions between complexes and solvent molecules in the previous Pd(II) complex are replaced by complex-complex interactions in the new Pd(II) complex, while BuOH and MeOH are interchangeable in the interactions within the crystal packing of the two Ni(II) complexes. Finally, solvent molecules are not involved in the crystal packing of the Cu(II) complex. The present study suggested that the solid state assembly of these systems is mainly driven by the molecular conformation, that depends in turn by the metal ion involved, while the solvent only plays a minor role.

The mechanical properties and stability of hydrophobic surface structures prepared by traditional methods are still the main technical bottlenecks restricting the broad application of hydrophobic systems on workpiece surfaces. In this contribution, we propose a technique called selective laser shock peening (SLSP) to enable large-scale high efficient, low-cost manufacturing of hydrophobic metal surfaces with enhanced mechanical properties for durable applications. Using the method of experimental investigation combined with numerical calculation, the hydrophobic properties, mechanical properties, and tribological properties of the samples prepared under SLSP, all-laser shock peening (ALSP), and non-laser shock peening (NLSP) are studied. The SLSP process could prepare a 3D gradient structure material with surface structures, a two-phase (strong phase, soft phase) distribution on the surface, and a multi-level gradient distribution in the thickness direction. Compared with the 2D gradient structure prepared by the traditional process, 3D gradient structures by SLSP have more significant advantages in improving the wetting behavior and the mechanical properties of the material, which proves SLSP to be a novel method to fabricate functional metal surface structures, with highly high engineering application value.

Safe administration of highly cytotoxic chemotherapeutic drugs is a challenging problem in cancer treatment due to the adverse side effects and collateral damage to non-tumorigenic cells. To mitigate these problems, new promising approaches, based on the paradigm of controlled targeted drug delivery (TDD), utilizing drug nanocarriers with biorecognition ability to selectively target neoplastic cells, are being considered in cancer therapy. Herein, we report on the design and testing of a nanoparticle-grid based biosensing platform to aid in the development of new targeted drug nanocarriers. The proposed sensor grid consists of superparamagnetic gold-coated core-shell Fe₂Ni@Au nanoparticles, further functionalized with folic acid targeting ligand, model thiolated chemotherapeutic drug doxorubicin (DOX), and a biocompatibility agent, 3,6,-dioxa-octanethiol (DOOT). The employed dual transduction based on electrochemical and enhanced Raman scattering detection have enabled efficient monitoring of the drug loading onto the nanocarriers, attached to the sensor surface, as well as the drug release under simulated intracellular conditions. The grid’s nanoparticles serve here as the model nanocarriers for new TDD systems under design and optimization. The superparamagnetic properties of the Fe₂Ni@Au NPs aid in nanoparticles’ handling and constructing a dense sensor grid with high plasmonic enhancement of the Raman signals due to the minimal interparticle distance.

Keywords: liquid alloys, microstratification, dispersed particles, spontaneous dispersion, criteria for true (entropic) spontaneous dispersion, mechanisms of quasi-spontaneous dispersion, methods and results for assessing size of dispersed particles.

Luminescent carbon dots (CDs) were locally synthesized in the core of CYTOP fibers using IR femtosecond laser direct writing (FLDW), a one-step simple method serving as a post-treatment of the genuine fiber. This approach enables the creation of several types of modifications such as ellipsoid voids. The CDs and photoluminescence (PL) distribute at the periphery of the voids. The PL spectral properties were studied through Excitation Emission Matrix in the visible range and excitation/emission spectrum in UV/visible range. Our finding reveals the presence of at least 3 distinct luminescent species, facilitating a broad excitation range extending from UV to green, and light emission spanning from blue to red. The average laser power and dose influence the quantity and ratio of these luminescent CD species. Additionally, we measured the spatially resolved lifetime of the luminescence during and after the irradiation. We found longer lifetimes at the periphery of the laser-induced modified regions and shorter ones closer to the center, with a dominant lifetime ~ 2ns. Notably, unlike many other luminophores, these laser-induced CDs are insensitive to oxygen, enhancing their potential for display or data storage applications.

The use of privileged scaffolds as starting point for the construction of libraries of bioactive compounds is a widely used strategy in drug discovery and development. Scaffold decoration, morphing and hopping are additional techniques that allow to modify the privileged framework chosen and better explore the chemical space around it. In this study, two series of highly functionalized pyrimidine and pyridine derivatives were synthesized by scaffold morphing approach of triazine compounds obtained previously as antiviral agents. Newly synthesized azines were evaluated against lymphoma, hepatocarcinoma, and colon epithelial carcinoma cells showing in five cases acceptable to good anticancer activity associated to low cytotoxicity on healthy fibroblasts. Finally, ADME in vitro studies were conducted on the best derivatives of the two series showing good passive permeability and resistance to metabolic degradation.

Biocomposite membranes based on polylactic acid (PLA) and cellulose nanocrystals (CNCs) were developed using a scientific approach. Dicumyl peroxide (DCP) was used as a polymerization ini-tiator, while tin octoate (Sn(Oct)2) and triphenylphosphane (P(C6H5)3) were used as catalysts. A torque rheometer was used to mix the components of the biocomposite, and thin films was prepared by solvent casting. Fourier transform infrared (FTIR) spectroscopy confirmed the coupling between the PLA and CNCs. Field emission scanning electron microscopy (FESEM) showed that the CNCs were well-dispersed in the PLA matrix with an unimodal particle size distribution and a maximum particle size of around 200 nm. Thermogravimetric analysis (TGA) and differential scanning calo-rimetry (DSC) analysis demonstrated good thermal stability and improved biodegradability of the biocomposite membrane compared to pure PLA. Mechanical characterization showed a Young's modulus of 1.65 GPa, which is comparable to that of other composite materials, and a maximum tensile strength of 20.31 MPa, which is higher than that of pure PLA. These results suggest that the developed biocomposite membrane has potential applications in water filtration, food packaging, and biomedical devices.

Heterometallic rare-earth clusters have garnered much attention because of their interest-ing solid-state structures and versatile applications in catalysis and material and polymer chemistry over the last four decades. Particular interest is rare earth–transition metal co-ordination compounds that behave as single-molecule magnets (SMMs) because of their potential use in information storage, spintronic devices, and magnetic refrigeration sys-tems. Another implementation involves using lanthanide clusters in luminescent-based sensing for environmental protection and security screening or in photocatalytic energy conversion reactions. Heterometallic rare earth complexes offer the promise of catalytic performance of many organic reactions due to their high oxygenophilicity, Lewis acidity, high coordination numbers, and ability to change the coordination environment quickly. Therefore, they are commonly applied as catalysts in asymmetric synthesis, oxidation re-actions, and CO2 conversions or as initiators in ring-opening polymerization and copoly-merization of cyclic monomers. They are also attractive single-source molecular precur-sors for functional inorganic materials. This review focused on the unique features and properties of the heterometallic rare earth complexes, which are closely correlated with their molecular structure. Our summary is a valuable resource, providing researchers with an insightful exploration of the heterometallic rare-earth complexes that demonstrated multimetallic synergy and cooperativity effects in various applications.

In this study, bioactive compounds present in chestnut shells (CS) - derived from the industrial peeling processing - were extracted through different procedures. The aqueous extracts were characterized and the highest extraction yield and total phenolic content was obtained by Conventional Liquid Extraction (CLE). Gallic and protocatechuic acids were the main simple phenols in the extract with 86.97 and 11.20 mg/g chestnut shells dry extract (CSDE), respectively. Six tumor cell lines (DU 145, PC-3, LNCaP, MDA-MB-231, MCF-7 and Hep G2) and one normal prostate epithelial cell line (PNT2) were exposed to increasing concentration of CSDE (1-100 µg/mL) for 24 h and cell viability was evaluated using MTT assay. A reduced rate in cell viability was observed in DU 145, PC-3, LNCaP and MCF-7 cells while viability of MDA-MB-231 and Hep G2 cells was not affected except for PNT2 cells at a concentration of 100 µg/mL. Furthermore, CSDE-at concentrations of 55.5 and 100 µg/mL- lead to a significant increase of apoptotic cells in DU 145 cells of 28.2% and 61%, respectively. In conclusion, our findings showed that CS might be used for the extraction of several polyphenols that may represent good candidates for alternative therapies or in combination with current chemotherapeutics.

A systematic study has been conducted on barbiturate complexes of all five alkali metals Li–Cs prepared from the metal carbonates or hydroxide in aqueous solution without other potential ligands present, varying the stoichiometric ratio of metal ion to barbituric acid (BAH). Eight polymeric compounds (two each for Na, K, and Rb and one each for Li and Cs) have been characterised by single-crystal X-ray diffraction. All contain some combination of barbiturate anion BA− (necessarily in a 1:1 ratio with the metal cation M+), barbituric acid, and water. All organic species and water molecules are coordinated to the metal centres via oxygen atoms as either terminal or bridging ligands. Coordination numbers range from 4 (for the Li complex) to 8 (for the Cs complex). Extensive hydrogen bonding plays a significant role in all the crystal structures, almost all of which include pairs of N–H…O hydrogen bonds linking BA− and/or BAH components into ribbons extending in one dimension. Factors influencing the structure adopted by each compound include cation size and reaction stoichiometry as well as hydrogen bonding.

Along time, many minted coins were withdrawn from circulation, being replaced with new ones. The returned obsolete metal coins were melted in order to sustainable reuse of the alloy for other purpose. Between the withdrawing and melting, some of the metal coins were cancelled by destruction of the original shape and dimension, using some adequate tools. In the first part, the paper is focused to present some aspects insight of the cancelling method used on the Romanian old nickel coins; also, there are presented some examples. The introductive part also includes the literature review in the field of coin manufacturing, covering the subjects as metal behavior under the striking load, aspects about the 3D modeling and FEM analysis or explaining some striking errors. Result the paper main purpose, to study the particularities of one or another cancelling method applied on subjected coins, which conducted to more or less valuable collection metal pieces. In the paper second part, is introduced the adequate 3D model, computed for the cancelling dies, respectively the coin. Then, there are introduced the assembled models, corresponding to each cancelling case, which consist by the obverse and reverse cancelling dies, having the coin inside them. For the each model, the finite element analysis is realized and is achieved for different initial conditions. The final part of the paper presents the analysis results and also the discussions and conclusions.

Transition metal complexes have historically played a pivotal role in creating vibrant pigments utilized across artistic mediums such as ceramics, paintings, and glass mosaics. Despite their extensive historical use, our understanding of the mechanisms governing transition metal complex behavior has predominantly emerged in recent times, leaving numerous aspects of this process ripe for exploration. These complexes exhibit striking color variations under diverse conditions when employed in pigment formulations. This review utilizes a bottom-up scientific approach, spanning from microscopic to macroscopic scales, to unravel the molecular origins of the colors generated by transition metal complexes in pigments and ceramic glazes. Advanced spectroscopy techniques and computational chemistry play pivotal roles in this endeavor, highlighting the significance of understanding and utilizing analytical data effectively, with careful consideration of each technique's specific application. Furthermore, the review investigates the influence of processing conditions on color variations, providing valuable insights for artists and manufacturers aiming to enhance the precision and quality of their creations while mitigating environmental impact.

A series of novel chiral nonmetallocene pincer-type rare earth metal dialkyl complexes bearing the chiral monoanionic tridentate C2-symmetric 1,3-bis(oxazolinymethylidene)isoindoline (BOXMI) ligand (BOXMI)Ln(CH2SiMe3)2 1-3 (1, Ln = Sc, yield = 57%; 2, Ln = Lu, yield = 55%; 3, Ln = Y, yield = 62%) have been prepared in moderate yields via the acid-base reaction between the BOXMI ligand and rare earth metal tri(trimethylsilylmethyl) complexes. The X-ray diffractions show that both of the complexes 1 and 2 contain one Boxmi ligand and two trimethylsilylmethyl ligands, adopting a distorted-trigonal-bipyramidal configuration. In the presence of cocatalyst such as borate and AlR3, these complexes 1-3 exhibit high activities up to 6.8 × 104 (g of polymer)/(molLn h) and high cis-1,4-selectivities up to 97%) in the polymerization of isoprene in toluene, yielding the cis-1,4-polyisoprenes with high molecular weights (Mn up to 710000 g/mol) and bimodal molecular weight distributions (Mw/Mn = 2.0-4.5).

Vigina radiata (Mung bean) is an important legume species belongs to the family Fabaceae, cultivated in varies region of Ethiopia for its nutritional values. The nutritional composition of the crop affected by different biotic and environmental stress which depends on growth environment. The aim of the present study was to determine the concentrations of selected heavy metals (Pb, Cu and Cr) in seed of mung bean collected from Shewarobit, Northcentral Ethiopia using inductively coupled plasma optical emission spectroscopy (ICP-OES). Acid digestion with HCl, HNO3 and HClO4 for 1hr at temperature of 90oC to 95oC by hot plate digester. The level of the heavy metals in the samples were 2.51 mg/L, Pb; 6.53 mg/L, Cu; and 0.38 mg/L, Cr respectively. The concentration of copper (Cu) in the seed of mung bean was higher than the other target metals (Pb and Cr) whereas, Cr occurred in least concentration. The overall accuracy of the method obtained from spiking experiment (recovery) was within the range 80 to 120%, which accounts 115.75%, 97.5%, 101.17% for Pb Cr and Cu respectively. Notably, these results indicating the reliability and applicability of the procedure for extraction of studied metals. The concentration of heavy metals in edible seed of mungbean is low as compared to WHO/FAO recommendation and absolutely safe for consumption in the study area. Thus, producer should follow similar agroecological managements of the crop production to maintain heavy metal concentration of such in the crop.

The chiral optical Tamm state (COTS) is a special localized state at the interface of a handedness-preserving mirror and a structurally chiral medium such as a cholesteric liquid crystal or a chiral sculptured thin film. The spectral behavior of COTS, observed as reflection resonances, is described by the temporal coupled-mode theory. Mode coupling is different for two circular light polarizations because COTS has a helix structure replicating that of the cholesteric. The mode coupling for co-handed circularly polarized light exponentially attenuates with the cholesteric layer thickness since the COTS frequency falls into the stop band. Cross-handed circularly polarized light freely goes through the cholesteric layer and can excite COTS when reflected from the handedness-preserving mirror. The coupling in this case is proportional to anisotropy of the cholesteric and theoretically it is only anisotropy of magnetic permittivity that can ultimately cancel this coupling. These two couplings being equal results in a polarization crossover (the Kopp--Genack effect) for which a linear polarization is optimal to excite COTS. The corresponding cholesteric thickness and scattering matrix for COTS are generally described by simple expressions.

This study aimed to obtain and characterize extracted hemp oil enriched in cannabidiol (CBD) by decarboxylation of cannabidiolic acid (CBDA) and to give new insights into its antioxidant and anticancer effects. Optimization of CBDA decarboxylation in hemp oil was performed, and CBD and CBDA contents and purities were determined by “flash chromatography”, 1H- and 13C-NMR. The antioxidant properties of CBD-enriched oil were investigated by Fe2+ chelating activity, Fe3+ reducing antioxidant power assay, O2− scavenging activity, HO− scavenging ability and lipid peroxidation inhibitory assay and its cytotoxicity, apoptosis- and oxidative stress-inducing effects on NHDF, MeWo, HeLa, HepG2 and HOS cells were determined. The CBD concentration in hemp oil was increased by CBDA soft decarboxylation optimized at 90°C, for 1 h and resulted oil was capable of reducing iron, scavenging free radicals, and inhibiting lipid peroxidation in cell-free oxidative conditions. CBD-enriched oil promoted NHDF proliferation at up to 15 µg CBD/mL, while inducing apoptosis and ROS production and modulating antioxidant enzymes’ gene expression in cancer cells, being selective for osteosarcoma cells and induced apoptosis by p53- and ROS-independent mechanisms. CBD-enriched hemp oil demonstrated antioxidant properties in oxidative conditions and promoted normal fibroblasts’ proliferation, while inducing apoptosis and ROS production in cancer cells.

Blood testing is a crucial medical application. In this study, we applied Raman spectroscopy to test blood samples and obtained complete biological information, including the main components and compositions in these samples. Short-wavelength (532-nm green light) Raman scattering spectroscopy was conducted on samples of normal blood, abnormal blood in 3 types of preparation including whole blood, plasma, and serum, and the underlying information reflected by the biological characteristics detected in each sample type were analyzed. Raman spectroscopy results indicated that normal blood had high hemoglobin content, which suggests that hemoglobin is a major component of blood. Hemoglobin affects blood oxygen level. The characteristic peaks of hemoglobin were observed at 690, 989, 1015, 1182, 1233, 1315, and 1562–1649 cm−1. Analysis of plasma and serum samples indicated the presence of β-carotene, which exhibited characteristic peaks at 1013, 1172, and 1526 cm−1. In addition, surface-enhanced Raman spectroscopy was used to collect biological signals that are difficult to obtain in conventional Raman spectroscopy, including those of small molecules such as hormones, antibodies, and enzymes. Changes in biological information collected in this manner can be used as a basis for potentially diagnosing clinical diseases.

Platinum(II) complexes have been found to be effective against cancer cells. Cisplatin curbs cell replication by interacting with the deoxyribonucleic acid (DNA), eventually leading to cell death and reducing cell proliferation. In order to investigate the ability of platinum complexes to affect cancer cells, two examples from the class of polyflurophenylorganoamidoplatinum(II) complexes were synthesised and tested on isolated DNA. The two compounds trans-[N,N’-bis(1,2,3,5,6-pentafluorophenyl)ethane-1,2-diaminato(1-)](2,3,4,5,6-pentafluorobenzoato)(pyridine)platinum(II) (PFB), and trans-[N,N’-bis(1,2,3,5,6-pentafluorophenyl)ethane-1,2-diaminato(1-)](2,4,6-trimethylbenzoato)(pyridine)platinum(II) (TMB) were compared with cisplatin through their reaction with DNA. Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy was applied to analyse the interaction of the Pt^(II) complexes with DNA in the hydrated, dehydrated and rehydrated state. These were compared with control DNA in acetone/water (PFB, TMB) and isotonic saline (cisplatin) under the same conditions. Principle Component Analysis (PCA) was applied to compare the ATR-FTIR spectra of the untreated control DNA with spectra of PFB and TMB treated DNA samples. Disruptions in the conformation of DNA treated with the Pt^(II) complexes upon rehydration were mainly observed by monitoring the position of the IR-band around 1711 cm^-1 assigned to the DNA base-stacking vibration. Furthermore, other intensity changes in the phosphodiester bands of DNA at ~1234 cm^-1 and 1225 cm^-1 and shifts in the dianionic phosphodiester vibration at 966 cm^-1 were observed. The isolated double stranded DNA (dsDNA) or single stranded DNA (ssDNA) showed different structural changes when incubated with the studied compounds. PCA confirmed PFB had the most dramatic effect by denaturing both dsDNA and ssDNA. Both compounds, along with cisplatin, induced changes in DNA bands at 1711, 1088, 1051 and 966 cm^-1 indicative of DNA conformation changes. The ability to monitor conformational change with infrared spectroscopy paves the way for a sensor to screen for new anticancer therapeutic agents.

Biocidal coatings are of great interest to the healthcare system. In this work, the biocidal activity of coatings based on a complex biocide containing polymer and inorganic active antibacterial c omponents was studied. Silver oxide was distributed in a matrix of a positively charged interpolyelectrolyte complex (IPEC) of polydiallyldimethylammonium chloride (PDADMAC) and sodium polystyrene sulfonate (PSS) using ultrasonic dispersion, forming nanoparticles with an average size of 5-6 nm. The formed nanoparticles in the matrix are not subject to agglomeration and changes in morphology during storage. It was found that the inclusion of silver oxide in a positively charged IPEC allows a 4-fold increase in the effectiveness of the complex biocide against E. coli K12 in comparison with the biocidal effect of PDADMAC and IPEC. Polycation, IPEC and the IPEC/Ag2O ternary complex form coatings on the glass surface due to electrostatic adsorption. Adhesive and cohesive forces in the resulting coatings were studied on micron-scale coatings using dynamometry. It was found that the stability of the coating is determined primarily by adhesive interactions. At the macro level, it is not possible to reliably identify the role of IPEC formation on adhesion. On the other hand, the use of the optical tweezers method makes it possible to analyze macromolecules in submicron scale and to evaluate the multiple increase in adhesive forces when forming a coating from IPEC compared to coatings from PDADMAC. Thus, the application of ternary IPEC/Ag2O complexes makes it possible to obtain coatings with increased antibacterial action and improved adhesive characteristics.

In this paper, the synthesis of two novel luminescent Eu3+ ion complexes [Eu(TFT)3(phen) (1) and Eu(TFT)3(bpy)•Hex (2)] based on the combination of 2-(2,2,2-trifluoroethyl)-1-tetralone (TFT), containing n-donor ligands (1,10-phenanthroline or 2,2'-Bipyridine) and Eu3+ ion is reported herein, and their structural features are discussed on the basis of X-ray crystallographic and thermal analyses. We observed that the ligands transfer energy effectively to the metal center by fluorescence, IR and UV spectrograms studies. The structures and properties of complexes 1-2 were optimized by the DFT theoretical calculation, and the calculation results were consistent with the experimental X-ray structure data and spectral analysis.

The band gap research in graphene is still a very important topic for materials application. Here, we report a band gap opening and p-type semiconducting property of the graphene by using an electrochemical doping on graphene surface. The manganese-oxide nanopar-ticles adsorbed on the graphene were used as the dopants in an electrolyte, which induce the band gap opening and the change of electronic structure. In addition, the fabricated graphene FET shows the p-type semiconductor behaviors. The temperature dependent conductivity of the p-type doped graphene at applied potential of 1.5 V during electro-chemical doping shows the formation of band gap of 0.23 eV, which is obtained from the fitting of conductivity equation. The semiconducting properties of manganese-oxide doped graphene is attributed to the formation of manganese-oxide nanoparticle on the surface of graphene.

Photodynamic therapy (PDT) has garnered significant attention in the fields of cancer treatment and drug-resistant bacteria eradication due to its non-invasive nature and spatiotemporal controllability. Iridium complexes have captivated researchers owing to their tunable structure, exceptional optical properties, and substantial Stokes displacement. However, most of these complexes suffer from aggregation-induced quenching, leading to diminished luminous efficiency. In contrast to conventional photosensitizers, photosensitizers exhibiting aggregation-induced luminescence (AIE) properties retain the ability to generate a large number of reactive oxygen species when aggregated. To overcome these limitations, we designed and synthesized a novel iridium complex named Ir-TPA in this study. It incorporates quinoline triphenylamine cyclomethylated ligands that confer AIE characteristics for Ir-TPA. We systematically investigated the photophysical properties, AIE behavior, spectral features, and reactive oxygen generation capacity of Ir-TPA. The results demonstrate that Ir-TPA exhibits excellent optical properties with pronounced AIE phenomenon and robust capability for producing singlet oxygen species. This work not only introduces a new class of metal iridium complex photosensitizer with AIE attributes but also holds promise for achieving remarkable photodynamic therapeutic effects in future cellular experiments and biological studies.

The Covid-19 pandemic has resulted in the closure of schools at every level, globally, forcing education to move online. Meeting the needs of students online for Science Lab classes, in particular, is a challenge since the physical labs are not available to the teachers or students. OLabs is a virtual Science Lab providing a complete learning environment of theory, experimental procedures, videos, animations, simulations, and assessments that capture real lab experiences with the relevant pedagogy. This study looks at the acquisition and behaviors of users, on the OLabs platform, during pre and Covid-19 times. Using Google Analytics, we observe that, during the pandemic time, users increasingly adopted OLabs as a new learning pedagogy for performing experiments as indicated by parameters like the number of users; the number of unique pages viewed per session; time spent on viewing content; bounce rate; and preference for content types such as theory, simulations, videos, and animations.

A lead zirconate titanate [PZT;Pb(Zr_0.52Ti_0.48)O₃] layer embedded infrared (IR) detector decorated with wavelength-selective plasmonic crystals has been investigated for high-performance non-dispersive infrared (NDIR) spectroscopy. A plasmonic IR detector with an enhanced IR absorption band has been designed based on numerical simulations, fabricated by conventional microfabrication techniques, and characterized with a broadly tunable quantum cascade laser. The enhanced responsivity of the plasmonic IR detector at specific wavelength band has improved the performance of NDIR spectroscopy and pushed the limit of detection (LOD) by an order of magnitude. In this paper, a 13 fold enhancement in the LOD of a methane gas sensing using NDIR spectroscopy is demonstrated with the plasmonic IR detector.

The effects of rare earth Ce on the microstructure and properties of cast pure copper were investigated through thermodynamic calculations, XRD analysis, mechanical testing, metallographic microscopy, and scanning electron microscopy (SEM). The experimental results demonstrate that the reaction between rare earth Ce and oxygen as well as sulfur in copper exhibits a significantly negative Gibbs free energy value, indicating a strong thermodynamic driving force for deoxidation and desulfurization reactions. Ce is capable of removing trace amounts of O and S from copper. Moreover, the maximum solid solubility of Ce in Cu falls within the range of 0.009% to 0.01%. Furthermore, Ce can refine columnar grains while enlarging equiaxed grains in as-cast copper.Upon addition of rare earth Ce, the tensile strength increased by 8.45%, elongation increased by 12.1%, and microhardness rose from 73.5HV to 81.2HV-an increase of 10.5%. Overall, rare earth Ce has been found to enhance both the microstructure and mechanical properties of cast pure copper.

Diesel is consistently a very popular fuel for internal combustion engines. Its consumption in the European Union has been rising over recent years, as has the number of engines increasingly sensitive to fuel contamination. One of the most important parameters affecting diesel quality is water content. Although its exceedances of the standard’s permissible amount are not common, they carry the risk of serious damage to expensive, modern fuel injection systems. Current methods of measuring water content require both specialised personnel and equipment, as well as transporting the sample to a suitable laboratory. The research presented in this paper was aimed at verifying whether it would be possible to test the moisture content of diesel using impedance spectroscopy. Once refined, such measurement method could be used in situ. Analysing the properties of diesel is challenging, mainly because many types of the fuel are sold, the chemical composition of which is always a well-guarded manufacturer’s secret. The experimental results obtained on many types of commercially available diesel show that it is possible to use impedance spectroscopy to estimate the water content of different types of diesel fuel. The measurement accuracy achieved makes it possible to detect approaching or exceeding the permissible water content.

Among the various types of gas sensors, the chemoresistive gas sensors based on metal oxides are considered the most attractive ones due to their simple operation, low costs and miniaturization. Thin films of V2O5 undoped and doped with TiO2 were studied as nitrogen dioxide, methane and hydrogen sensors. The experimental kinetics of the electrical conductivity changes due to introduction and removal of gas on metal oxide gas sensors were successfully explained in terms of the Langmuir adsorption theory.

The primary goal of picture compression is to reduce the amount of unused image data while still storing or transmitting it in a format that is appropriate. The compression of raw binary data is quite different from the compression of a picture, and these differences may be rather substantial. In light of this, compression is often regarded as an essential technique for the purposes of both data storage an d transmission in order to mitigate the excessive amounts of data that are generated by these images. In order to transmit enormous datasets, particularly for the purposes of telemedicine and teleradiology, one needs a significant amount of storage capacity as well as an expansive network. As a result, compression is an important aspect of medical imaging. In addition to the importance of compression, the quality of the photos themselves is also an essential factor in the success of analysis. In addition to this, the amount of time necessary to compress the photographs before sending them should be reduced.

Polyhedral oligomeric silsesquioxane (POSS) is a suitable nanoscale reinforcement for thermosetting polymers, such as epoxy resin systems in order to modify its mechanical, thermal, and chemical properties. The inclusion of POSS in the epoxy resin at higher loading (greater than 1 wt.%), however, introduces the ductility during the fracture behavior of these nanocomposites. Consequently, the J-integral is used to quantify the fracture behavior of these materials and characterize the crack growth resistance curve against stable crack growth. A range of nanocomposites is prepared by adding 0.5, 1, 3, 5, and 8 wt.% of glycidyl POSS into DGEBF epoxy resin cured with an amine-based curing agent. From the fracture toughness experiment the load-displacement result confirms that when the POSS reinforcement is greater than 1 wt.%, the fracture behavior of the nanocomposite changes from brittle to ductile. For both brittle and ductile nanocomposites, the addition of POSS molecules improves the crack initiation toughness. The development of POSS–POSS compliant domains are reported previously, is attributed for this change in the failure behavior. The fractured images of POSS–epoxy nanocomposites, obtained using scanning electron microscopy, show that the increase in fracture resistance at higher values of POSS loading occurs due to the extensive shear yielding. Meanwhile, the increased fracture toughness at lower values of POSS loading occurs due to crack pinning and crack deflection.

Perovskite Solar Cell (PSC) is a third-generation photovoltaic device known for its rapid improvement in efficiency levels over the past decade. Moreover, the added benefits of abundant sourcing of raw materials, uncomplicated fabrication process, organic and inorganic device materials, and tuneable bandgaps make this technology a sustainable energy alternative. However, the efficiency values of these devices are subjected to variation depending on factors such as material compatibility, environmental conditions, energy band alignment of device components and stability characteristics to extrinsic and intrinsic factors. One such vital intrinsic factor is film morphology, homogenous and superior film quality formation and pinhole and trap-free films. In this study, we have investigated the formation of perovskite films on a qualitative basis using metal chloride washing of salts such as Erbium, Antimony, Cadmium and Chromium Chloride. The study aims to analyse the difference in film formation with various metal chloride washing and how this could potentially impact or contribute to photovoltaic performance if the devices are fabricated.