Search Results (123)

In this study, we aimed to determine the chemical constituents of M. seguinii, which led to the isolation and identification of 26 compounds. Three new prenylated dihydrobenzofurans [myrsinoic acids I (1), J (2), and K (3)] and a new flavonoid glycoside, mearnsetin 3-O-α-L-arabinopyranoside (4), were discovered, and the absolute configuration of the known compound, myrsinoic acid B (5), was re-established. To ensure the structural accuracy of these compounds, comprehensive spectroscopic analyses were performed, including one- and two-dimensional nuclear magnetic resonance spectroscopy, mass spectrometry, and circular dichroism spectroscopy. In addition, computational analysis methods such as density functional theory (DFT)-based Electronic Circular Dichroism (ECD) simulations and Gauge-Including Atomic Orbitals (GIAOs) ¹H and ¹³C NMR chemical shift calculations with DP4+ probability analysis were utilised to further support the structural assignments. Full article

New technology has opened opportunities for research and exploration of deep-water ecosystems, highlighting deep-sea coral reefs as a rich source of novel bioactive natural products. During our ongoing investigation of the chemodiversity of the Irish deep sea and the soft coral Anthothela grandiflora, we report 12 unreported cadinene-like functionalized sesquiterpenes, anthoteibinenes F–Q. The metabolites were isolated using both bioassay- and ¹H NMR-guided approaches. One-/two-dimensional NMR spectroscopy and high-resolution mass spectrometry were used for structure elucidation, while a combination of NOESY NMR experiments, GIAO NMR calculations coupled with DP4+ probabilities measures, and ECD comparisons were incorporated to propose relative and absolute configurations of the anthoteibinenes. The metabolites were screened against the Respiratory Syncytial Virus (RSV), ESKAPE pathogens, five Candida albicans strains, and one strain of C. auris. Full article

Hanoi is the capital of Vietnam, with a total area of 3359.82 km² and a population of about 8.4 million people. This is one of the most developed cities in Vietnam, with an urbanization rate of 60%. In this study, we investigated how developed and urbanized areas may influence lichen diversity in Hanoi. The lichen community from Hanoi was studied using three tree stands from each of five landscapes: natural vegetation, industrial parks, urban and rural areas, and roadsides. Lichen species and their cover abundance were recorded on tree trunks at heights from 30 to 150 cm above ground in ten host trees that were randomly selected for each replication. Sixty-seven lichen species, from sixteen families and eight orders, were recorded. Results showed urbanization and the development of industrial parks and transportation altered species composition, evidenced by a reduced number of lichen species. Natural forests sustained the highest lichen diversity measured. These results suggest that a greater diversity of lichen can be preserved in natural forests, if that natural vegetation is effectively managed and conserved. Full article

Cathinone and its synthetic derivatives belong to organic compounds with narcotic properties. Their structural diversity and massive illegal use create the need to develop new analytical methods for their identification in different matrices. NMR spectroscopy is one of the most versatile methods for identifying the structure of organic substances. However, its use could sometimes be very difficult and time-consuming due to the complexity of NMR spectra, as well as the technical limitations of measurements. In such cases, molecular modeling serves as a good supporting technique for interpreting ambiguous spectral data. Theoretical prediction of NMR spectra includes calculation of nuclear magnetic shieldings and sometimes also indirect spin–spin coupling constants (SSCC). The quality of theoretical prediction is strongly dependent on the choice of the theory level. In the current study, cathinone and its 12 fluorinated derivatives were selected for gauge-including atomic orbital (GIAO) NMR calculations using Hartree–Fock (HF) and 28 density functionals combined with 6-311++G** basis set to find the optimal level of theory for ¹H, ¹³C, and ¹⁹F chemical shifts modeling. All calculations were performed in the gas phase, and solutions were modeled with a polarized-continuum model (PCM) and solvation model based on density (SMD). The results were critically compared with available experimental data. Full article

The Portuguese Institute for Quality is responsible for the realization and dissemination of the frequency standard in Portugal. There are several techniques for frequency transfer, but we use a frequency mixer to detect phase variations between two light signals with different wavelengths, traveling along an optical fibre. In this paper, we present the development of a digital twin (DT) that replicates the use of a frequency mixer to improve the frequency transfer problem. A setup was built to train and validate the technique: a frequency mixer was used to determine the phase difference between the two signals, which are caused by temperature gradients in the fibre, together with real-time temperature data from sensors placed along the fibre and on the mixer itself. The DT was trained with two machine learning algorithms, in particular, ARIMA and LSTM networks. To estimate the accuracy of the frequency mixer working as a phasemeter, several sources of uncertainty were considered and included in the DT model, with the goal of obtaining a phase value measurement and its uncertainty in real time. The JCGM 100:2008 and JCGM 101:2008 approaches were used for the estimation of the uncertainty budget. With this work, we merge DT technology with a frequency mixer used for phase detection to provide its value and uncertainty in real time. Full article

The present study investigated the ¹H Nuclear Magnetic Resonance (NMR) spectra of hydrogen-rich water (HRW) produced using the EVObooster device. The analyzed HRW has pH = 7.1 ± 0.11, oxidation–reduction potential (ORP) of (−450 ± 11) mV, and a dissolved hydrogen concentration of 1.2 ppm. The control sample was tap water filtered by patented technology. A 600 NMR spectrometer was used to measure NMR spectra. Isotropic 1H nuclear magnetic shielding constants of the most stable clusters (H₂O)_n with n from 3 to 28 have been calculated by employing the gauge-including-atomic-orbital (GIAO) method at the MPW1PW91/6-311+G(2d,p) density function level of theory (DFT). The HRW chemical shift is downfield (higher chemical shifts) due to increased hydrogen bonding. More extensive formations were formed in HRW than in control filtered tap water. The exchange of protons between water molecules is rapid in HRW, and the ¹H NMR spectra are in fast exchange mode. Therefore, we averaged the calculated chemical shifts of the investigated water clusters. As the size of the clusters increases, the number of hydrogen bonds increases, which leads to an increase in the chemical shift. The dependence is an exponential saturation that occurs at about N = 10. The modeled clusters in HRW are structurally stabilized, suggesting well-ordered hydrogen bonds. In the article, different processes are described for the transport of water molecules and clusters. These processes are with aquaporins, fusion pores, gap-junction channels, and WAT FOUR model. The exponential trend of saturation shows the dynamics of water molecules in clusters. In our research, the chemical shift of 4.257 ppm indicates stable water clusters of 4–5 water molecules. The pentagonal rings in dodecahedron cage H₃O⁺(H₂O)₂₀ allow for an optimal arrangement of hydrogen bonds that minimizes the potential energy. Full article

The structure of the title compound (4d), unexpectedly obtained in the reaction between o-phenylenediamine and 2-benzoylcyclohexanone instead of the target 3H-benzo[b][1,4]diazepine derivative 3d, was determined spectroscopically in solution and by a single-crystal X-ray diffraction (XRD) study. It involves two enantiomeric rotamers, called forms D and U, of which the structure was elucidated based on NMR spectra measured and predicted in DFT-GIAO calculations. An averaging of δ_Cs for all tautomeric positions in the benzimidazole part of the 4d hydrate studied in wet (probably slightly acidic) CDCl₃ unambiguously indicates tautomeric exchange in its imidazole unit. An XRD analysis of this material confirms the existence of only one tautomer in the solid phase. The non-covalent interactions forming between molecules of water and benzimidazole derivative are shorter than the sum of van der Waals radii and create an infinite-chain hydrogen bond motif along the b-axis. A possible mechanism for the observed cyclocondensation is also proposed. Full article

Expeditionary studies of the functioning of landscapes of mid-mountain monsoon (including fog) forests have been being conducted within the landscape and ecological station in the territory of the Bidoup-Nui Ba National Park and the adjacent Hon Giao since 2018 and are currently underway. One of the research objectives is to clarify the biogeochemical migrations of the material composition of soils in the “leaf debris–soil” system. We have consistently studied natural objects for their material composition as well as the intensity and rate of involvement of chemical elements in physicochemical migration processes in the “leaf debris–soil” system. Our findings indicate an active influx of a select group of examined elements (Se, Pd, Ag, Cd, Sn, Bi), particularly Bi, Pd, Se, and Cd, through the leaf debris and the detachment of aboveground plant organs, warranting their integration into organogenic soil horizons. Subsequently, lateral migration (Pd, Cd, Se) ensues. Slope processes within subordinate landscape facets, in addition to soil moisture and aeration processes, contribute to the subsequent redistribution of elemental volumes introduced into organogenic soil horizons. Full article

The design and synthesis of analogs of natural products can be a valuable source of medicinal preparations for the pharmaceutical industry. In the present study, the structural elucidation of eleven derivatives of 2,4-dihalogeno substituted synthetic analogues of the natural compound carvacrol was carried out by means of NMR experiments, and of another thirteen by DFT calculations. By selective NOE experiments and the irradiation of CH signals of the isopropyl group, individual conformers were assigned as syn and anti. By comparing GIAO/B3LYP/6-311++G(d,p)-calculated and experimentally measured vicinal ³J_CH spin-spin constants, this assignment was confirmed. An unusual relationship is reported for proton-carbon vicinal couplings: ³J_CH (180°) < ³J_CH (0°). The conformational mobility of carvacrols was studied by 2D EXSY spectra. The application of homonuclear decoupling technique (HOBS) to these spectra simplifies the spectra, improves resolution without reducing the sensitivity, and allows a systematic examination of the rotational barrier of all compounds via their CH signals of the isopropyl group in a wider temperature interval. The rate constants of the isopropyl rotation between syn and anti conformers were determined and the corresponding energy barriers (14–17 kcal/mol) were calculated. DFT calculations of the energy barriers in carvacrol derivatives allowed the determination of the steric origin of the restricted isopropyl rotation. The barrier height depends on the size of the 2- and 4-position substituents, and is independent of the derivatization of the OH group. Full article

Salmonella enterica subsp. enterica serovar Enteritidis (S. Enteritidis) is one of the leading causes of foodborne infections associated with broilers and laying hens. Portugal has had the lowest notification rates of salmonellosis in recent years, due to the vaccinations of layer and breeder flocks and strict compliance with biosecurity measures. However, data about the genetic diversity of S. Enteritidis in Portugal are scarce. In this study, 102 S. Enteritidis isolates selected from human (n = 63) and non-human sources (n = 39) were characterized by serotyping, antimicrobial susceptibility, and whole genome sequencing. The S. Enteritidis population was mainly resistant to fluoroquinolones, and a sole isolate showed resistance to extended-spectrum cephalosporins. ST11 was the most frequent sequence type, and three novel STs from human isolates (ST9236, ST4457, and ST9995) were assigned. Several Salmonella pathogenic islands (SPI) and Putative SPI were present in the genomes, namely SPI-1, 2, 3, 4, 5, 9, 10, 12, 13, and 14, C63PI, CS54_island, and 170 virulence genes were identified. The phylogenetic analysis revealed that strains from Portugal are genetically heterogeneous regarding sample type, collection date, and genetic content. This study increases the available data, essential to a better characterization of strains in a global context. Full article

NMR fingerprints are valuable tools for analyzing complex natural product mixtures and identifying incorrectly assigned structures in the literature. Our diagnostic NMR fingerprints for formyl phloroglucinol meroterpenoids revealed discrepancies in the structures reported for eucalyprobusal C (1a) and eucalypcamal K (2a). NMR fingerprinting PCA analyses identified 1a as an oxepine-diformyl phloroglucinol and 2a as an oxepine 3-acyl-1-formyl phloroglucinol, contrary to their initial assignments as pyrano-diformyl and pyrano 3-acyl-1-formyl phloroglucinols, respectively. Extensive reinterpretation of their reported one- and two-dimensional NMR data, coupled with GIAO DFT-calculated ¹H and ¹³C NMR chemical shift and DP4+ analyses, supported the unequivocal reassignment of eucalyprobusal C to 1b and eucalypcamal K to 2b. The absolute configurations of the revised oxepine-containing phloroglucinol meroterpenoids were confirmed via the reinterpretation of their reported ROESY and NOESY NMR data, along with comparative TDDFT-calculated and experimental ECD spectra. Full article

Detecting the boundaries of geologic structures is one of the main tasks in interpreting gravity anomalies. Many methods based on the derivatives of gravity anomalies have been introduced to map the source boundaries. The drawbacks of traditional methods are that the estimated boundaries are divergent or false boundaries appear in the output map. Here, we use the exponential transform of the tilt angle of the horizontal gradient to improve the edge detection results. The robustness of the presented method is illustrated using synthetic data and real examples from the Voisey’s Bay Ni-Cu-Co deposit (Canada) and the Tuan Giao (Vietnam). The findings show that the presented technique can produce more precise and clear boundaries. Full article

Koninginins X-Z (1–3), three novel polyketides, were isolated from the solid fermentation of the endophytic fungus Trichoderma koningiopsis SC-5. Their structures, including the absolute configurations, were comprehensively characterized by a combination of NMR spectroscopic methods, HRESIMS, ¹³C NMR, DFT GIAO ¹³C NMR, and electronic circular dichroism calculations as well as single crystal X-ray diffraction. In addition, all the compounds were evaluated for antifungal activity against Candida albicans. Full article

Carnarvon is a key horticultural district in Western Australia which is located approximately 900 km north of Perth and is characterised by a semi-arid climate. In Carnarvon, capsicum (Capsicum annuum L.) is the second most important vegetable crop after tomato, with approximately 3700 tonnes of capsicum fruit produced annually with a farm gate value of AUD 13.5 million. High temperatures, excessive sunlight, low air humidity, and strong wind in spring and summer are major impediments to the achievement of high yield and quality of capsicum in this region. Capsicums are usually planted between March (early autumn) and May (late autumn), and the harvest is usually finished by October (spring) of the same year when grown under shade net houses. However, the internal microenvironment in the shade net houses is sub-optimal for the crop in the early and late growing season due to excessive temperatures and low humidity, resulting in a shorter harvest window and lower production. This study was conducted to examine the possibilities to extend the cropping season for capsicum varieties (i.e., Chevello and Chevi) grown under the retractable roof production system (RRPS) and explore an alternative protected cropping structure that is more affordable and suitable to grow vegetable crops under Carnarvon weather conditions. Overall, the results showed that capsicums planted in February (planting 1) performed better than specimens planted later on in the season: planting 1 performed better and yielded the highest marketable fruit yield (102.6 t ha⁻¹) compared to those planted in early April (planting 2, 72.5 t ha⁻¹) and late May (planting 3, 36.1 t ha⁻¹). The RRPS effectively mitigated the adverse weather conditions and provided a more optimised internal microenvironment for vigorous crop establishment in late summer and an extended harvest in late spring, leading to a higher marketable fruit yield per crop. The total soluble solids were cultivar-specific, with the Brix level of Chevello changing with planting time while those of Chevi remained constant. The study identifies the potential for an alternative protected cropping structure, i.e., the modified multi-span polytunnels. The technical feasibility and affordability of the alternative protected cropping structure is also discussed. Full article

Betaines of squaric acid have gained research interest because of their structural and spectral properties. We elucidated the crystal and molecular structure of the triethylammonium betaine of squaric acid (1) by X-ray crystallography, IR, and NMR spectroscopy augmented by Hirshfeld surface analysis and DFT calculations. The crystal structure determination using Hirshfeld atom refinement reveals that the resonance hybrid structure with partial enolate character of the two lateral squaric acid C=O groups describes 1 best. The solid-state supramolecular structure features weak intermolecular C−H···O hydrogen bonds. The number of C=O bands in the IR spectrum in the solid-state is consistent with local C_2v symmetry of the squaric acid residue in 1. The ¹³C NMR signals of this group in solution were assigned based on 2D NMR experiments and computational prediction using the Gauge-Independent Atom Orbital (GIAO) method. The present study provides the first structural characterization of a betaine of squaric acid containing a four-coordinate nitrogen atom directly attached to the four-membered ring. Full article