Spectroscopic Data Research Articles

High-resolution spectroscopy of detached eclipsing binaries during total eclipses

We present results of high-resolution spectroscopic observations of detached eclipsing binaries (DEBs) with total eclipses, for which UVES spectra were obtained during the phase of totality. These observations serve as a key way to determine the age and initial metallicity of the systems and to verify evolutionary phases of their components and distances. With the additional, independent information concerning the effective temperature and metallicity of one of the components, we aim to estimate the precise ages of the studied binaries and show the usefulness of totality spectra. The second goal was to provide precise orbital and physical stellar parameters of the components of systems in question. Using the VLT/UVES, we obtained high-resolution spectra of 11 DEBs during their total-eclipse phase. Atmospheric parameters of then-visible (larger) components were obtained with With additional spectroscopy from the Comprehensive Research with \'Echelles on the Most interesting Eclipsing binaries ( project, public archives, and literature, we obtained radial-velocity (RV) measurements, from which orbital parameters were calculated. Photometric time-series observations from TESS and ASAS were modelled with the JKTEBOP code, and, combined with RV-based results, they allowed us to obtain physical parameters for nine double-lined systems from our sample. All the available data were used to constrain the ages with our own approach, utilising MESA isochrones. Reddening-free, isochrone-based distances were also estimated and confronted with Gaia Data Release 3 (GDR3) results. We show that single spectroscopic observations taken during a total eclipse can break the age-metallicity degeneracy and allow for the precise determination of the age of a DEB. With high-quality spectroscopic and photometric data, we are able to reach a 5-10<!PCT!> level of uncertainty (e.g. $724^ $ Myr). Even for single-lined DEBs, where absolute masses are not possible to obtain, the spectroscopic analysis of one of the components allows one to put strong constraints on the properties of both stars. For some cases, we noted inconsistencies between isochrone-based and GDR3 distances. For one binary, which could not be fitted with a single isochrone (RZ Eri), we suggest a new explanation.

The Insecticidal Activity of Secondary Metabolites Produced by Streptomyces sp. SA61 against Trialeurodes vaporariorum (Hemiptera: Aleyrodidae).

Trialeurodes vaporariorum Westwood poses a significant threat to vegetable and ornamental crops in temperate zones, resulting in notable reductions in yield and substantial economic burdens. In order to find compounds with high insecticidal activity against T. vaporariorum, five compounds were isolated and identified from the crude extract of Streptomyces sp. SA61. These include three new polyketides, named strekingmycins F-H (1-3); one new diterpenoid, named phenalinolactone CD8 (4); and one known compound, strekingmycin A (5). Their structures were analyzed using high-resolution electrospray ionization mass spectrometry and one-dimensional and two-dimensional nuclear magnetic resonance spectroscopy data and by comparing them with previously reported data. The insecticidal activities of compounds 1-5 against T. vaporariorum were evaluated. Among them, compound 5 exhibited the highest insecticidal activity, with an LC50 of 6.949 mg/L against T. vaporariorum at 72 h using the leaf-dip method. Lower insecticidal activities were found in compounds 1-4, with LC50 values of 22.817, 19.150, 16.981 and 41.501 mg/L, respectively. These data indicate that strekingmycin could be a potential candidate for a novel insecticide to control T. vaporariorum.

Effect of detachment on Magnum-PSI ELM-like pulses: Direct observations and qualitative results

Abstract Conditions similar to those at the end of the divertor leg in a tokamak were replicated in the linear plasma machine Magnum-PSI. The neutral pressure in the target chamber is then increased to cause the target to transition from an attached to a detached state. Superimposed to this steady state regime, ELM-like pulses are reproduced, resulting in a sudden increase in plasma temperature and density, such that the heat flux increases transiently by half an order of magnitude. 
Visible light emission, target thermography, and Thomson scattering are used to demonstrate that the higher the neutral pressure the more energy is removed from the ELM-like pulse in the volume. If the neutral pressure is sufficiently high, the ELM-like pulse can be prevented from affecting the target and the plasma energy is fully dissipated in the volume instead (ID 4 in Table 1). The visible light images allow the division of the ELM-plasma interaction process of ELM energy dissipation into 3 "stages" ranging from no dissipation to full dissipation (the target plasma is detached).
In the second publication related to this study, spectroscopic data is analysed with a Bayesian approach, to acquire insights into the significance of molecular processes in dissipating the plasma energy and particles.

The spatially resolved relation between dust, gas, and metal abundance with the TYPHOON survey

Abstract We present the spatially resolved relationship between the dust-to-gas mass ratio (DGR) and gas-phase metallicity (Zgas or 12+log(O/H)) (i.e., DGR–Zgas relation) of 11 nearby galaxies with a large metallicity range (1.5 dex of 12+log(O/H)) at (sub-)kpc scales. We used the large field-of-view (≳ 3′) optical pseudo-Integral Field Spectroscopy data taken by the TYPHOON/PrISM survey, covering the optical size of galaxies, combining them with multi-wavelength data (far-UV to far-IR, CO, and H i 21 cm radio). A large scatter of DGR in the intermediate metallicity galaxies (8.0 < 12+log(O/H)< 8.3) is found, which is in line with dust evolution models, where grain growth begins to dominate the mechanism of dust mass accumulation. In the lowest metallicity galaxy of our sample, Sextans A (12+log(O/H)< 7.6), the star-forming regions have significantly higher DGR values (by 0.5–2 dex) than the global estimates from literature at the same metallicity but aligns with the DGR values from metal depletion method from Damped Lyman Alpha systems and high hydrogen gas density regions of Sextans A. Using dust evolution models with a Bayesian MCMC approach suggests: 1) a high SN dust yield and 2) a negligible amount of photofragmentation by UV radiation, although we note that our sample in the low-metallicity regime is limited to Sextans A. On the other hand, it is also possible that while metallicity influences DGR, gas density also plays a role, indicating an early onset of dust grain growth in the dust mass build-up process despite its low metallicity.

Intramolecular Vibrational Energy Redistribution in the Reaction H3+ + CO → H2 + HCO.

An ab initio direct molecular dynamics (MD) calculation at the RS2/aug-cc-pVQZ level, followed by vibration mapping, has been applied to the H3+ + CO → H2 + HCO+ reaction to elucidate the intramolecular vibrational energy redistribution (IVR) processes during the reaction. Direct MD calculations were carried out for 20 K (a typical temperature for interstellar dark clouds) and 330 K (a typical translational temperature for ions in a glow discharge). Under the Cs symmetry constraint, the approach of H3+ turned out to be the H-C stretching mode of the [H···CO]+ part, which invoked the C-O stretching and then the H-C-O bending modes. Under no symmetry constraint, a strong bending mode was first invoked, and the intensities of the subsequent H-C and C-O stretching modes were kept relatively small. The detailed analyses of the IVR during the reaction, in terms of vibration mixing, gave a clue to understanding experimentally observed anomalies in the bending modes, such as population inversion at some bending states. In the MD simulation at 20 K, less than two-thirds of the reaction energy was converted to the vibrational energy of the resultant HCO+ part and one-third to the translational and rotational energies of the leaving H2 molecule. These direct MD simulations, when combined with the experimental spectroscopy data, shed light on a clear understanding of the reaction mechanism, including the IVR during the reaction.

Cytotoxic diterpenoids from the roots of Euphorbia jolkinii Boiss against human pancreatic cancer SW1990 cells by regulating the expressions of Bcl-2, Bax, and Caspase-3 proteins

Sixteen undescribed diterpenoids were identified from Euphorbia jolkinii Boiss, a widespread invasive plant in the grassland ecosystem of subalpine meadows in southwest China, through a combination of spectroscopic data analysis. These included two casbane diterpenoids (1 and 2), two ent-atisane diterpenoids (3 and 4), and twelve ent-isopimarane diterpenoids (5–16). All isolates were evaluated the cytotoxicity on pancreatic cancer SW1990 cells in which compounds 1 and 9 exhibited obvious bioactivities against the tumor cells with the IC50 values of 26.50 ± 6.36 and 21.09 ± 5.98 μM respectively. Moreover, compounds 1 and 9 were found to promote the pre-apoptosis of SW1990 cells and regulate the expressions of Bcl-2, Bax, and Caspase-3 proteins to display anti-tumor abilities. Compounds 1 and 9 were subjected to Bcl-2 protein via molecular ducking to reveal their anti-tumor mechanism further. The druggability prediction showed that they possessed good drug properties with development and utilization scenarios.

Tuning the atomic ordering of AFI framework with templates charge

In this work, AlPO4-5 (AFI) zeotype materials were synthesized using the microwave approach in the presence of two organic templates i.e. tripropylamine (R) and tetrapropylammonium (R+). The long- and short-range crystalline order of the samples were investigated by considering the effect of the template's charge on the atomic-level ordering of the AFI framework. Using advanced NMR spectroscopy, we shed the light on the importance of templates' role on the organization of the inorganic framework of aluminophosphates. The spectroscopic data clearly show a wider distribution of Al and P environments in the materials synthesized with the charged template (R+) due to the need of hydroxyl groups charge compensators that induce some bridges distortions. When a charged molecule (R+) was used, aluminum appears to be responsible for the charge compensation mechanism via the association of OH groups, impacting the environment of phosphorus as well. The hydroxyl groups needed for charge compensation in samples synthesized with R+ persist after calcination. Consequently, the hydrophilicity of the sample synthesized with R+ features approximatively two times higher values compared to the one synthesized with R.

Characterization and solubility measurement of synthetic uranophane and sklodowskite under oxic groundwater conditions

Naturally occurring uranyl silicates can serve as solubility-limiting solid phases (SLSPs) of U(VI) in the oxic environment of granitic groundwater, which is likely to occur in crystalline host rock media in Korea. In this study, two synthetic uranyl silicates, uranophane (Ca[UO2SiO3OH]2·5H2O) and sklodowskite (Mg[UO2SiO3OH]2·6H2O) were prepared and used to measure the U(VI) solubility in simulated groundwater (sGW), mimicking the composition of samples collected from the underground research tunnel at the Korea Atomic Energy Research Institute (KAERI). The solid- and solution-phase species involved were examined in detail using various characterization methods. According to the powder X-ray diffraction pattern and elemental analysis results, the synthetic mineral phases, which were identified as uranophane-α and sklodowskite having layered crystal structures, were retained intact in sGW; however, in 0.1 M NaClO4, emergence of other solid phases was observed. Enhanced FTIR and Raman spectroscopic data, particularly in the regions of 790–860 and 940–1020 cm−1 for the UO22+ and SiO44− ions, respectively, enable monitoring the changes in the solid phases. Ternary Ca–U(VI)-tricarbonato complexes were identified as the dominant dissolved U(VI) species in sGW using time-resolved laser-induced luminescence spectroscopy. Furthermore, the solubility constant of uranophane was calculated (log Ks,0° = 10.3 ± 0.4) and compared with the predicted values based on our geochemical modeling analysis and previously reported ones.

Applicability domain of a calibration model based on neural networks and infrared spectroscopy

Artificial neural networks are used as calibration models in routine analytical determinations that involve spectroscopic data. To ensure that the model will generate reliable predictions for new samples, the applicability domain must be well defined. This article describes a strategy for establishing the limits of the applicability domain when the calibration model is a feed-forward neural network. The applicability domain was defined by two limits: 1) the 0.99 quantile of the squared Mahalanobis distance calculated from the network activations of the training set and 2) the 0.99 quantile of the reconstruction error of the training spectra using either an autoencoder network or a decoder network. A new sample with a squared Mahalanobis distance and/or spectral residuals beyond these limits is said to be outside the applicability domain, and the prediction is questionable. The approach was illustrated by predicting the density of diesel fuel samples from mid-infrared spectra and the fat content in meat from near-infrared spectra. The methodology could correctly detect anomalous spectra in prediction using either the autoencoder or the decoder.

Exploring the activation potential of heme for 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol

The presence of chlorophenols in water poses a significant threat to human health and the environment. In response to this issue, a study was undertaken to evaluate the catalytic capabilities of chlorinated Heme towards common chlorophenols present in water, such as 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol. The study employed the B3LYP method, a sophisticated computational technique within density functional theory, to investigate the molecular interactions and transformations involved. It scrutinized structural parameters, Wiberg Bond Indices, which offer insights into the strength and nature of chemical bonds, along with spectroscopic data including infrared vibrational spectra, ultraviolet-visible absorption spectra, and molecular fluorescence spectra. Furthermore, the research analyzed molecular binding energies and orbital energy levels before and after the formation of complexes between Heme and the targeted chlorophenols. The findings indicate that Heme displays a notable activation characteristic towards these chlorophenols. This suggests that Heme could act as an effective catalyst in the degradation of chlorophenols in water, presenting a novel approach to water purification. The theoretical insights derived from this study are invaluable, potentially guiding the development of more efficient catalytic systems for treating chlorophenol-contaminated water, thereby reducing the environmental and health risks associated with these hazardous compounds.

Study on the chemical components and anti-neuroinflammatory activity of the roots of Clausena excavate Burm. f.

The ethanol extract of the roots of Clausena excavata gave two previously undescribed coumarins, clauexcatin A (1) and clauexcatin B (2), as well as a pair of new isomers, trans/cis-clauexcatin C (3a, 3b), along with thirty known compounds. Among these, compound 33 was isolated from this genus for the first time. The structures of these compounds were elucidated based on their physicochemical properties and spectroscopic data. The anti-neuroinflammatory activities were assessed using LPS-activated BV-2 microglial cells. Compounds 6, 8, 17, 24, 29, and 30 exhibited significant inhibition of nitric oxide release in a dose-dependent manner, with their inhibitory effects being 1.2 to 10.9 times greater than that of the positive control (minocycline).

Synthesis, single crystal study, molecular docking, and in vitro anticancer screening of a series of isoxazolone derivatives of chlorovinyl benzalaldehydes

A series of isoxazole derivatives (2a-i) were synthesized by conventional method using various substituted chlorovinyl benzaldehydes as precursors. Structures of all the synthesized compounds were confirmed by spectroscopic data (1H NMR, FTIR, HRMS). Single crystal X-ray study of four compounds was carried out. Molecular docking study was performed and the compounds were screened for in vitro anticancer activity. The results show that compounds with no substituent or smaller substituents on benzene ring have significant antiproliferative activity against tested cell line i.e. MCF7.

Three undescribed phenylbutenoids derivatives from Zingiber cassumunar Roxb. rhizomes and their biological activities

Phenylbutenoids belong to polyphenolic compounds that have demonstrated distinctive biological activities and are primarily characterised in the genus Zingiber (Zingiberaceae) species. From the EtOAc extract of the rhizomes of Zingiber cassumunar Roxb., three phenylbutenoid-type compounds, cassudimin B (1), cassumunol O (2), and cassumunol P (3), were isolated, along with five known compounds (4–8). Their structures were characterised through spectroscopic evidence and reference data. Biological activity investigation revealed that compounds 4, 5, and 8 exhibited promising potential for anti-α-glucosidase with IC50 values of 151.5, 180.1, and 39.5 µM, respectively, surpassing the positive control acarbose (IC50, 190.6 µM). Additionally, compounds 3–8 displayed cytotoxic effects on HepG2 cells ranging from 12.0 to 293.2 µM.

Geochemical evidence of drying during the 4.2 ka event in sediment cores from the Yucatán Peninsula, Mexico

Tropical hydroclimate variability during the Middle and Late Holocene was investigated using geochemical indicators of local-scale precipitation and evaporation preserved in sediment cores from two sites in the Mexican Yucatán Peninsula. Scanning X-Ray fluorescence spectroscopy data show generally decreasing precipitation trends during the Early and Middle Holocene. During the transition between the Middle and Late Holocene, geochemical evidence of reduced watershed erosion and increased evaporation indicate that a centennial-scale drying event impacted the region between 4.3 and 4.0 ka (kilo-anum; thousand years before present). These findings suggest that the 4.2 ka drying event, which has been previously recorded in Europe, Asia, and North and South America, also impacted the northern Neotropics. A comparison between our data and existing regional hydroclimate records suggests that dry conditions during the 4.2 ka event were coherent across western Central America. The timing of these regionally dry conditions coincided with a reduction in zonal sea surface temperature gradients in the tropical Pacific Ocean and a consequent mean-state increase in the frequency of El Niño events, suggesting that linkages between Pacific Ocean-atmosphere dynamics played a significant role in the regional drying that occurred during that time. These data provide new support for a Central American expression of the 4.2 ka event, evidence for which is currently rare.

3D Model for Representation and Visualization of Magnetic Resonance Spectroscopy Data

3D Model for Representation and Visualization of Magnetic Resonance Spectroscopy Data

LC–MS coupled with diagnostic ion strategy facilitated the discovery of 5-methylcoumarin meroterpenoids from Gerbera piloselloides

Plant-derived natural products remain crucial in drug development. However, the identification of undescribed natural products is becoming increasingly challenging. A comprehensive strategy combining LC–MS with diagnostic ions was proposed for the discovery of undescribed 5-methylcoumarin meroterpenoids. Thirteen undescribed 5-methylcoumarin meroterpenoids, including five pairs of enantiomers (1a/1b and 5a/5b–8a/8b), were isolated from the whole plant of Gerbera piloselloides. Their structures and absolute configurations were unambiguously determined based on their spectroscopic data, calculated and experimental ECD data and X-ray diffraction analysis. Bioassays conducted on scopolamine-induced injury PC12 cells revealed that compounds 5a/5b, 7a/7b and 8a/8b possessed mild protective effects. Additionally, compounds 2 and 8 showed notable IL-6 inhibition in lipopolysaccharide-induced BEAS-2B cells.

Chemical constituents from a soil fungus Xylaria sp. Y01 and their anticancer potential

Fifteen compounds, namely three new cytochalasans, one new sesquiterpenoid, two new amides, eight known cytochalasans, and one known amide, were isolated from the rice medium fermented by a soil fungus Xylaria sp. Y01. The structures of these compounds were determined through comprehensive analyses of their extensive spectroscopic data, along with quantum chemical calculations. In vitro cytotoxicity assays, we selected three cancer cell lines (HCT116, 4T1, and MHCC97H) and one normal human gastric epithelial GES-1 cell line to explore their potential as anticancer agents. As a result, 6,7-dihydro-7-oxo-cytochalasin C, 5,6-dihydro-7-oxo-19,20-epoxycytochalasin C, 19,20-epoxycytochalasin D, and 19‑epi-cytochalasin P1 showed cytotoxicity against GES-1, while only 19,20-epoxycytochalasin D also exhibited cytotoxicity against 4T1. Our findings further enrich the structural diversity of secondary metabolites from Xylaria species and provide clues for exploring their anticancer potential.

Anti-inflammatory bicyclic polyprenylated acylphloroglucinols with diverse architectures including an unprecedented 6/6/6 tricyclic core from Garcinia yunnanensis

Garciyunnanol A (1), an unprecedented 1,2-seco-bicyclic polyprenylated acylphloroglucinol (BPAP) possessing a unique 6/6/6 tricyclic core, was characterized from Garcinia yunnanensis together with 16 BPAPs, including eight new compounds (garciyunnanols B–I, 2–9). Biogenetically, the bicyclo[3.3.1]nonane-2,4,9-trione moiety of 12 reconstructed the bicyclic δ-lactone core of 2 through Norrish type Ⅰ cleavage and cyclization, followed by a cyclization of two side chains to form an intriguing 6/6/6 tricyclic core of 1. Their structures were elucidated through analysis of spectroscopic data, calculation and comparison of ECD spectra. Bioactivity evaluation manifested that compounds 1, 2, 5, 6 and 14 demonstrated superior inhibition of NO production compared to the positive control dexamethasone. Notably, compound 5 exhibited a dose-dependent inhibitory effect on NO production, with an IC50 value of 0.25 ± 0.87 µM. Furthermore, experiments involving ELISA, Western blotting, and immunofluorescence staining revealed that 5 effectively reduced the secretion of interleukin-1β in LPS plus nigericin-stimulated THP-1 macrophages by inhibiting the activation of the NLRP3 inflammasome.

NMR-Based Analysis of Cellular Central Energy Metabolism and Exchange Rates.

Cell cultures are widely used in studies to gain mechanistic insights of metabolic processes. The foundation of these studies lies on the quantification of intracellular and extracellular metabolites, and nuclear magnetic resonance (NMR) is one of the key analytical platforms used to this aim. Among the factors influencing the quality of the produced data are the sampling procedures as well as the acquisition and processing of spectroscopic data. Here we provide our workflow for obtaining quantitative metabolic data from adherent mammalian cells using NMR spectroscopy. The described protocol is compatible with other analytical methods like LC- or GC-MS-based lipidomics and untargeted metabolomics from the same sample. We also show how the collected extracellular data can be used to extract exchange flux rates, particularly useful for flux analysis studies and metabolic engineering of human-induced pluripotent stem cells.

Green Method of Doping Photochromic TiO2

The doping process is a unique method of changing the microstructure of a material, influencing its mechanical, thermal, and optical properties. Typically, the doping process is carried out via chemical reagents. In this work, we present a “green” method of doping photochromic TiO2 via low-temperature plasma. The doping agent was the electrode material that was sputtered during plasma burning. The process of electrode sputtering is confirmed by the emission spectroscopy data of the plasma zone and the mass loss of the electrodes. The doping process was confirmed by X-ray, Raman spectroscopy, and XPS analyses. The role of the dopant nature and the action of diaphragm discharge in improving the photochromic properties of titanium dioxide is considered.