Search Results (482)

A novel ocellatin-P1 isoform was isolated and purified from the skin secretion of the pepper frog Leptodactylus labyrinthicus. The crude skin secretion was fractionated by reversed-phase high-performance liquid chromatography (RP-HPLC) using a C₈ column and the peptide was subsequently purified on a reversed-phase C₁₈ column. Ocellatin-LB3 (as this isoform was named) was chemically sequenced by Edman degradation. This peptide is a linear C-terminally amidated molecule composed of 25 amino acid residues: ¹GLLDTLKGAAKNVVGGLASKVMEKL²⁵-NH₂. Synthetic ocellatin-LB3 was active against Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa and inactive against Staphylococcus aureus, Staphylococcus epidermidis and Enterococcus faecalis. In addition, the peptide reduced the Trypanosoma cruzi infection in L6 cells. At 64 µM it did not reduce erythrocytes or polymorphonuclear leukocytes, but did reduce mononuclear leukocyte counts, as detected by flow cytometry. No hemolytic activity was observed in red blood cells even at 128 µM. The peptide exhibited limited antiproliferative activity against MCF-7 and HeLa tumor cells at 128 µM. Pre-incubation with the peptide appeared to enhance N-formylmethionine-leucyl-phenylalanine (fMLP)-induced migration, indicating a potential additive or synergistic effect on human neutrophils. The three-dimensional structure of ocellatin-LB3 was investigated by circular dichroism (CD) and nuclear magnetic resonance (NMR). In the presence of sodium dodecyl sulfate (SDS), the peptide adopts an α-helical structure spanning residues Leu³–Lys²⁴, which remains largely preserved even at 95 °C. NMR Hydrogen/Deuterium (H/D) exchange experiments suggest that ocellatin-LB3 adopts a preferential orientation when interacting with SDS micelles. Based on the similarity among ocellatins, and on the physicochemical and structural properties of this peptide, a possible membrane-mediated mode of action is proposed, although this remains to be experimentally validated. Full article

The fractures of Weixinan oil shale simultaneously influence drilling fluid invasion and solid strength and makes the collapse pressure difficult to predict. The indentation–NMR combined experiments were conducted to analyze the collapse characteristics, and the relationship between water porosity and shale strength was established. The experiment results show that water infiltration still occurs in oil-based drilling fluids in the short term and leads to a significant strength decrease. 3D numerical modeling was used to analyze water migration and shale strength weakening under fluid–solid coupling. It was found that fractures act as seepage channels and this aggravates the clay hydration and the shale instability. This causes high collapse pressure under specific well inclination angles and azimuth angles. The research results provide important references for shale wellbore stability analysis and engineering practice with complex geostress conditions and hydration. Full article

The DIGIT experiment was launched at the Tournemire Underground Research Laboratory (URL) with the aim of determining the effects of temperature on the transfer of tracers mimicking the most mobile radionuclides in the Toarcian clay rock. The properties of this rock are similar to those of the host rocks being considered for a future deep geological repository for high-level radioactive waste (HLW). The experiment involves the monitoring of the interaction between a test water doped with stable halides and deuterium at constant concentration, and the porewater of the Toarcian clay rock under constant ambient conditions, as well as at higher temperature induced by artificial heating. This experiment seeks to partially address questions regarding the potential spread of contaminants during the thermal phase of HL waste packages. Specifically, the in situ experiment aims to evaluate the role of scale effects, thermodiffusion, a process that combines Fick’s law, the Soret effect, and convection in the transfer of radionuclides. This paper is the second part of a companion paper dedicated to predictive calculations and the installation of the experimental device. It presents the main experimental and modeling results obtained since the beginning of the installation and after 20 months of heat at 70 °C. The test was carried out in five phases, finishing with a sampling campaign: a phase 0 called “initial conditions”, followed by a pure diffusion phase (5 months), then three phases in a heated period lasting 1 year and 8 months. In total, 47 rock cores were analyzed, with approximately 170 samples tested by four diffusion methods (radial, outgoing, through and in vapor-phase) to determine the tracer concentrations in the porewater, their water content and their diffusive transport parameters. The results show a decrease in tracer concentrations with distance from the test zone, in the directions parallel and perpendicular to the stratification. The anisotropy of the medium results in greater migration in the direction parallel to the stratification. Thermal properties also confirm anisotropy with a higher thermal conductivity in the direction parallel to the stratification. Finally, an activation energy of 22.9 ± 1.7 kJ·mol⁻¹ could be proposed by NMR for deuterium, indicating diffusion behavior following an Arrhenius law between 30 and 70 °C. The experimental data allowed for the calibration of a 2D axisymmetric numerical model using the commercial finite element software COMSOL Multiphysics^®. The Fick’s law corrected by an Arrhenius law best reproduces the penetration of deuterium and anions. The Soret effect, integrated into certain scenarios, is only significant for anions’ migration, using a fitted Soret coefficient of 0.1 K⁻¹, as proposed in the literature for the Callovo-Oxfordian, the host rock of the Cigéo project in the east of France. The calibration of the simulated data with the experimental data allowed for the characterization of damaged and/or disturbed zones evolving over time. Simulations over 150 years, the duration of the thermal maximum for HLW packages, show that advection—modeled by Darcy’s law—would have a negligible role in this context due to the low permeability of the upper Toarcian. In conclusion, the DIGIT test showed that, for the Upper Toarcian clay rocks at the Tournemire URL in France, diffusion, corrected for the effect of temperature, is the mechanism that characterizes the transport of radionuclide analogues. The study showed that thermodiffusion has a limited influence on deuterium migration but remains significant for anions in the case of a coupling between temperature correction and thermodiffusion. The test also highlighted the impact of temperature on the spatiotemporal development of a damaged and/or disturbed zone. These new and relevant results in the field will need to be confirmed later through additional experiments. Full article

Fufang Yinhua Jiedu Granules (FFYHG) is usually applied to treat influenza and the common cold. However, there is no available report concerning the effects of chemical constituents in FFYHG on antiviral activity. In our study, four new terpenoid derivatives (1–4) and seventeen known compounds were isolated from FFYHG. Their structures and absolute configurations were determined by various techniques, including high-resolution mass spectrometry analysis, 1/2-dimensional (1D/2D) nuclear magnetic resonance (NMR) analysis, comparative electronic circular dichroism (ECD) studies (experiment vs. calculation), and acid hydrolysis. In addition, the inhibitory effects of twenty-one isolated compounds against influenza A viruses (H1N1) including A/California/07/2009 (CA07) and A/WSN/1933 (WSN) strains were evaluated in vitro, and compound 4 exhibited a moderate inhibitory effect on CA07 strain, with a half maximal inhibitory concentration (IC₅₀) value of 37.10 ± 1.35 μM. This study enhanced the understanding of the active ingredients in FFYHG against influenza virus, providing a foundation for further research on the material basis and quality control of FFYHG. Full article

Tight sandstone reservoirs are characterized by highly heterogeneous pore structures, in which multiscale pore–throat systems jointly control the shapes of capillary pressure curves and relative permeability, thereby exerting a fundamental influence on water production behavior and the overall development performance of gas reservoirs. The Ordos Basin is generally characterized by the development of tight sandstone. The tight sandstones exhibit porosities of 2–13% and permeabilities of 0.01–10 × 10⁻³ μm². To quantitatively elucidate the controlling mechanisms of multiscale pore structure on capillary pressure curve morphology and relative permeability, this study systematically investigates the fractal and multifractal characteristics of pore structures in tight sandstones based on high-pressure mercury intrusion (MICP) and nuclear magnetic resonance (NMR) experimental data, and establishes a quantitative relationship between fractal parameters and the capillary pressure curve shape parameter λ. First, capillary pressure curves were fitted using the Brooks–Corey model within the effective saturation interval to extract the shape parameter λ, which characterizes the concentration degree of pore-size distribution and the drainage behavior. Subsequently, based on NMR T₂ spectra, the small-pore fractal dimension D₁, large-pore fractal dimension D₂, and the multifractal singularity spectrum width Δα were extracted to quantitatively describe the geometric complexity of pore structures at different scales. On this basis, the correlations between λ and D₁, D₂, and Δα were systematically analyzed, and the predictive performance of λ under different parameter combinations was compared. The results indicate that: (1) the pore structures of tight sandstones exhibit pronounced fractal and multifractal characteristics at the NMR T₂ scale, with significant differences among samples; (2) λ shows an overall negative correlation with fractal parameters, among which the correlations with the large-pore fractal dimension D₂ and the multifractal spectrum width Δα are the most significant; (3) compared with models using a single fractal dimension, the multiparameter model incorporating Δα provides a more comprehensive characterization of multiscale pore heterogeneity, leading to a substantial improvement in the accuracy and stability of λ prediction; and (4) λ exerts a clear control on the shape of relative permeability curves, where a larger λ corresponds to earlier initiation and forward-shifted rising segments of water-phase flow, while a smaller λ results in overall flatter relative permeability curves. From the perspectives of fractal and multifractal theory, this study establishes an intrinsic linkage among pore structure, capillary pressure curve shape parameters, and relative permeability, providing a novel quantitative framework for constraining relative permeability curve morphology in tight sandstones under conditions where systematic relative permeability experiments are unavailable. Full article

Nuclear Magnetic Resonance (NMR) spectroscopy has long been a cornerstone in the structural elucidation of molecules, offering unique insights into atomic-level connectivity, conformation, and dynamics. Over the past decades, methodological and technological advances have significantly expanded its capabilities and applications. This manuscript charts the evolution of NMR from classical 1D/2D experiments to modern methods empowered by ultrahigh magnetic fields, cryogenic probes, non-uniform sampling, new methodologies, and hyperpolarization. We emphasize the growing synergy between experiment and computation, where automated analysis, quantum chemical calculations, and machine learning are dramatically enhancing the accuracy and efficiency of structure determination. We also highlight NMR’s broadening scope in areas ranging from complex mixtures and natural products to biomolecular and materials science. Full article

Sugarloaf chicory (Cichorium intybus var. porphyreum) represents a valuable crop for investigating metabolic responses to environmental stress. This study applied quantitative ¹H-NMR-based metabolomics to characterize the water-soluble metabolome and evaluate root metabolic adaptations under water-deficit (WD) conditions compared to well-watered (WW) conditions. A total of 44 compounds were identified across roots and leaves, with inulin being root-specific. To address the lack of aqueous NMR data for chicory sesquiterpene lactones (STLs), a solid-phase extraction and fractionation protocol was implemented. Comparison of ¹H-NMR and ¹³C chemical shifts with data from the literature, 2D NMR experiments (HSQC, HMBC), and spiking with standards confirmed that the major root STLs (lactucin, 8-deoxylactucin, and lactucopicrin) are 15-oxalate conjugates with enhanced water solubility. Under water deficit, root profiles revealed significant stress-induced alterations: sucrose, alanine, threonine and phospho-choline increased, whereas asparagine, glutamic acid, chiro-inositol, myo-inositol, and all three STL conjugates decreased markedly (−39% to −50%). These shifts reflect adaptive osmotic adjustments and carbon reallocation strategies under stress. As roots represent a remarkable source of bioactive STLs, these findings support their potential valorization as functional ingredients. This study establishes quantitative NMR metabolomics as a robust tool for assessing physiological responses to water deficit, providing insights into stress adaptation mechanisms and identifying roots as promising targets for alternative applications. Full article

CO₂ geological sequestration in marine sediment is one of the important ways to lower carbon emissions. To study the influence of CO₂ sequestration on the permeability and porosity of unconsolidated strata, this paper conducted overpressure permeability, isothermal adsorption and CO₂ displacement experiments. Through nuclear magnetic resonance (NMR) technology, the effects of supercritical CO₂ (SCO₂) at different temperatures on the permeability evolution and pore size variation of unstratified strata in marine hydrate reservoirs were studied. The experimental results show that: (1) When the pressure changed from 0 to 17.5 MPa, the permeability and porosity of the soil samples decreased sharply. The porosity dropped from 36.83% to 16.07%, and the permeability also decreased from 48.53 mD to 1.18 mD. (2) During the adsorption tests, the fitted absolute adsorption capacity of CO₂ and CH₄ gradually increased with pressure growth. The maximum fitted absolute adsorption capacity of CO₂ was 2.45 times that of CH₄. (3) Through displacement experiments, the porosity and permeability increments during SCO₂ displacement were much greater than those during non-SCO₂ displacement. From 30 °C to 70 °C, the increments of porosity and permeability all increased. After SCO₂ displacement, the pores’ proportions (>0.1 μm) increased for all samples, with the largest growth rate reaching 34.37%. Above all, these results indicate that environmental pressure significantly affects the permeability of soil samples, and that SCO₂ displacement can effectively enhance the proportion of large-sized pores, thereby further improving the permeability of unconsolidated strata. Full article

This work presents a detailed study of the coordination of Eu(III) with tartrate and oxalate ligands in aqueous solutions. The following techniques were employed: potentiometric titrations, 1D ¹H, ¹³C multinuclear NMR spectroscopy, 2D NMR experiments (COSY, HMQC, HMBC), and UV-Vis spectroscopy. Overall (cumulative) formation constants (logβ) were determined at ionic strengths of 0.1, 0.5, and 1.0, M KNO₃ over the temperature range 298–318 K. At 298 K, the oxalate complexes are significantly more stable (logβ = 7.63→15.70 as the ionic strength increases from 0.1 to 1.0 M) than the corresponding tartrate species (logβ = 5.11→8.87). Analysis of the temperature dependence of logβ shows that the Gibbs free energy change comprises both temperature-dependent terms and an approximately temperature-independent covalent contribution, the latter becoming strongly negative values in the tartrate system. The NMR data support a bidentate coordination mode involving deprotonated hydroxyl and carboxylate groups, whereas ¹⁷O NMR monitors the mechanism of water exchange within the Eu(III) hydration sphere. In the UV-Vis domain, a distinct blue shift in the absorption band is observed at 0.1 M KNO₃, while at 1.0 M KNO₃, the band shows a pronounced decrease in intensity, a hypochromic effect. This behavior can be attributed to increased structural distortion and a partial loss of coplanarity within the tartrate coordination environment. By contrast, the oxalate system behaves differently: the spectra, together with the thermodynamic data, support a more covalent Eu–O interaction, consistent with stabilization of Eu(III) by two dicarboxylate ligands adopting distinct coordination modes. Full article

Background/Objectives: Studying the role of UV-induced metabolic changes in skin physiology, and especially skin diseases, has gained importance in both medicine and cosmetics. With the development of new technologies, a variety of approaches have been implemented to model these metabolic effects. In this study, we explore the reproducibility of the UVA1-induced metabolic changes observed in different in vitro, ex vivo, and in vivo systems with escalating complexity. Our aim is to elaborate on the role of experimental setups in the reliable representation of in vivo data in other systems. Methods: Metabolic profiles post UVA1 treatment were assessed in skin cell culture, skin explants, and intact skin. For cell culture and explants, the metabolites from the culture medium were assessed via 1D-CPMG NMR. Intact skin samples were collected via microdialysis and the resulting dialysate was measured with GC–TOF-MS. Results: Data show that, despite great metabolic variations between the systems, several metabolites, such as glutamic acid, succinic acid, and threonine, change in a similar manner across multiple systems after UVA1 irradiation, including in vivo settings. Some metabolites, like phenylalanine, citric acid, and pyruvic acid, show similar UVA-mediated metabolic patterns between corresponding in vitro and ex vivo systems, but do not overlap well with in vivo data. Conclusions: Our findings emphasize the need for a metabolite-by-metabolite approach when deciding on the proper experimental system to perform UV irradiation experiments with regard to cutaneous physiology. Full article

Three new pyrrole alkaloids, streptopyrroles D–F (1–3), along with four known analogs (4–7) were isolated from Sea Anemone-Associated Streptomyces sp. S1502 via an OSMAC (One Strain Many Compounds)-based strategy. Their structures were elucidated through comprehensive spectroscopic analyses, including HRESIMS and 1D/2D NMR experiments (COSY, HSQC, and HMBC), and further confirmed by X-ray crystallography. Biological evaluation identified streptopyrrole (4) as an anti-MRSA (methicillin-resistant Staphylococcus aureus) agent, while 4 and 6 displayed broad-spectrum cytotoxicity and good selectivity against a panel of human cancer cell lines. Notably, 4 and 6 showed particularly potent activity against the lung cancer cell lines H1299, SW1573, and A549, with IC₅₀ values ranging from 5.43 to 16.24 μM. Further mechanistic investigation revealed that both compounds suppress the proliferation of lung cancer cells by inducing cell cycle arrest at the G₀/G₁ phase and impair metastatic potential by inhibiting migration and invasion. These findings not only expand the structural diversity of marine-derived pyrrole alkaloids but also reveal the anticancer mechanisms of 4 and 6, highlighting their promise as active candidates for further antitumor drug development, particularly in lung cancer. Full article

In search of natural and safe compounds with immunomodulatory effects, this study identified a glucan with a molecular weight (Mw) of 1.2 × 10⁷ Da, named MSP-1-1, which was extracted and purified from Morchella sextelata via water extraction, alcohol precipitation, and column chromatography. Based on comprehensive characterization using HPAEC, SEC-MALLS-RI, FT-IR, GC-MS, NMR, and SEM, a structural model for MSP-1-1 is proposed. The model depicts a glucan with a backbone predominantly composed of →4)-α-D-Glcp-(1→ linkages, featuring occasional →4,6)-α-D-Glcp-(1→ residues that serve as branch points. The branches are identified as single α-D-Glcp-(1→ units attached at the O-6 position of these branching residues. In vivo experiments revealed that MSP-1-1 restored cyclophosphamide-induced abnormalities in immune organ indices, histology, and peripheral blood parameters. Additionally, MSP-1-1 significantly enhanced macrophage phagocytosis, splenic lymphocyte proliferation, and the proportions of CD3⁺CD4⁺ and CD3⁺CD8⁺T cells, while increasing the CD3⁺CD4⁺/CD3⁺CD8⁺ ratio. It also elevated concentrations of IgA and IgM in both serum and thymus, indicating immunomodulatory activity. In summary, this research elucidated the structural characteristics and immunomodulatory activity of MSP-1-1, providing insights into the bioactivity of M. sextelata glucan and a basis for further exploring its potential functional applications. Full article

Does position matter? In many respects, it certainly does, but does it also matter in the case of a functional group such as 4-diethylaminophenyl in the structure of phenanthro[9,10-d]imidazole derivatives? We attempt to answer this question in this article by considering selected physicochemical properties of the presented compounds. Therefore, in this work, four phenanthro[9,10-d]imidazole derivatives (AM-0–AM-3) were obtained by Debus-Radziszewski condensation. All derivatives were purified, and their structures were confirmed using NMR spectroscopy. The synthesized compounds were then compared for their thermal, electrochemical, and optical properties. This demonstrated that the derivatives (AM-0 and AM-1) containing a 4-diethylaminophenyl substituent at the C2 position exhibit better physicochemical parameters than the other compounds, particularly in terms of thermal stability, energy gap, and even quantum yield. In the case of the latter parameter, derivatives containing 4-diethylaminophenyl at the C2 position show an increase of up to 15–30% (depending on the solvent used) compared to the compound containing the considered substituent at N1. The obtained research results were compared with DFT calculations to gain a deeper understanding of the experiments performed. Full article

To address the challenges of strong heterogeneity and poor crude oil mobility in tight conglomerate reservoirs of the Mahu Oilfield, this study systematically evaluated the effects of different surfactants on wettability alteration, spontaneous imbibition, and relative permeability through high-temperature/high-pressure spontaneous imbibition experiments, online Nuclear Magnetic Resonance (NMR) monitoring, and relative permeability measurements. Core samples from the Jinlong and Madong areas (porosity: 5.98–17.55%; permeability: 0.005–0.148 mD) were characterized alongside X-Ray Diffraction (XRD) data (clay mineral content: 22–35.7%) to compare the performance of anionic, cationic, nonionic, and biosurfactants. The results indicated that the nonionic surfactant AEO-2 (Fatty Alcohol Polyoxyethylene Ether) (0.2% concentration) at 80 °C exhibited optimal performance, achieving the following results: 1. a reduction in wettability contact angles by 80–90° (transitioning from oil-wet to water-wet); 2. a decrease in interfacial tension to 0.64 mN/m; 3. an imbibition recovery rate of 40.14%—5 to 10 percentage points higher than conventional fracturing fluids. NMR data revealed that nanopores (<50 nm) contributed 75.36% of the total recovery, serving as the primary channels for oil mobilization. Relative permeability tests confirmed that AEO-2 reduced residual oil saturation by 6.21–6.38%, significantly improving fluid flow in highly heterogeneous reservoirs. Mechanistic analysis highlighted that the synergy between wettability reversal and interfacial tension reduction was the key driver of recovery enhancement. This study provides a theoretical foundation and practical solutions for the efficient development of tight conglomerate reservoirs. Full article

Thiourea and structurally related urea derivatives are widely recognised for their ability to transport anions through hydrogen bonding interactions. The strength of these interactions correlates with the electronegativity of the ligand and the acidity of the NH hydrogens involved. Thiourea, being more acidic than urea, exhibits partial deprotonation in the presence of certain anions such as organic carboxylates, fluoride, and bromide, while remaining resistant to deprotonation by chloride. This behaviour suggests a degree of selectivity toward chloride ions. Additionally, while carbamide-containing molecules tend to aggregate—potentially reducing their ion-binding efficiency—thiourea derivatives show reduced aggregation, preserving their binding capabilities. In this study, we report the synthesis and characterisation of 21 novel thiourea derivatives obtained by reacting 2-aminobenzoylamino acid esters with various substituted phenyl isothiocyanates. Seven similar thiourea-containing molecules were made as a comparison—without the amino acids—by reacting aniline with the different phenyl isothiocyanates. The reaction kinetics were found to be influenced primarily by the electronic nature of the substituents on the phenyl ring. Electron-withdrawing groups (EWGs), such as para-nitro, 3,5-bis(trifluoromethyl), and fluorine, accelerated the reaction, while electron-donating groups (EDGs), such as para-methoxy, slowed it down. Interestingly, the nature of the amino acid precursors had no significant impact on reaction time; however, reactions with aniline proceeded the fastest. Solvent choice also played a role: reactions in N,N-dimethylformamide (DMF) proceeded faster than in acetone, although with reduced yields. Consequently, reaction conditions were optimised to balance time efficiency and product yield. To evaluate the chloride ion-binding properties of the synthesised compounds, ¹H NMR titration experiments were conducted in deuterated dimethyl sulfoxide (DMSO-d₆). The association constants (K_a) derived from these studies revealed a clear correlation with the electronic nature of the substituents. Compounds bearing EWGs exhibited enhanced chloride binding, while those with EDGs showed diminished binding affinity. Surprisingly, the presence of amino acid moieties led to a decrease in K_a values, despite the electron-withdrawing nature of the amide groups. This suggests that steric or conformational factors may play a role in modulating binding strength. Overall, the synthesised thiourea derivatives demonstrate mild, reversible chloride ion-binding behaviour, making them promising candidates for further development as selective anion receptors. The insights gained from this study contribute to a deeper understanding of structure–activity relationships in anion-binding systems and may inform the design of future supramolecular architectures with tailored ion recognition properties. Full article