Search Results (80)

The dynamic process of water depletion plays a critical role in both surface coalbed methane (CBM) development and underground gas extraction, reshaping water–rock interactions and inducing complex permeability responses. Addressing the limited understanding of the coupling mechanism between heterogeneous pore water evolution and permeability during dynamic processes, this study simulates reservoir transitions across four zones (prospective planning, production preparation, active production, and mining-affected zones) via centrifugal experiments. The results reveal a pronounced scale dependence in pore water distribution. During low-pressure stages (0–0.54 MPa), rapid drainage from fractures and seepage pores leads to a ~12% reduction in total water content. In contrast, high-pressure stages (0.54–3.83 MPa) promote water retention in adsorption pores, with their relative contribution rising to 95.8%, forming a dual-structure of macropore drainage and micropore retention. Multifractal analysis indicates a dual-mode evolution of movable pore space. Under low centrifugal pressure, D₋₁₀ and Δα decrease by approximately 34% and 36%, respectively, reflecting improved connectivity within large-pore networks. At high centrifugal pressure, an ~8% increase in D₀−D₂ suggests that pore-scale heterogeneity in adsorption pores inhibits further seepage. A quantitative coupling model establishes a quadratic relationship between fractal parameters and permeability, illustrating that permeability enhancement results from the combined effects of pore volume expansion and structural homogenization. As water saturation decreases from 1.0 to 0.64, permeability increases by more than 3.5 times. These findings offer theoretical insights into optimizing seepage pathways and improving gas recovery efficiency in dynamically evolving reservoirs. Full article

Olive leaves, the main byproducts of olive cultivation, are characterized by a plethora of bioactive metabolites with significant nutritional value. Their main pentacyclic triterpenes, Oleanolic Acid (OA) and Maslinic Acid (MA), are two high added-value compounds with remarkable activities. This study aimed to develop an efficient methodology for extracting and purifying OA and MA, utilizing Supercritical Fluid Extraction (SFE) and Centrifugal Partition Chromatography (CPC)—two modern, scalable, and green techniques. A total of 21 g of olive leaves were subjected to SFE using supercritical CO₂ and ethanol as co-solvent. The extraction employed a step gradient mode, starting with 100% CO₂ and incrementally increasing ethanol (0–10% w/w) every 20 min. Fractions rich in OA and MA (500 mg) were further purified via CPC, utilizing pH zone refining to exploit the protonation and deprotonation properties of acidic triterpenes. The biphasic solvent system consisted of n-hexane, ethyl acetate, ethanol, and water (8:2:5:5 v/v/v/v), with trifluoroacetic acid added to the stationary phase and triethylamine added to the mobile phase. This two-step process yielded 89.5 mg of OA and 28.5 mg of MA with over 95% purity, as confirmed by HPLC-ELSD and ¹H-NMR. Moreover, purified compounds and SFE fractions exhibited promising elastase and collagenase inhibition, highlighting them as dermocosmetic agents. Full article

Reduced-molar-mass low-acyl gellan gum was obtained by the centrifugation of an aqueous solution of commercially available food-grade gellan gum. The derived sample was characterized by NMR, FTIR, ICPE, and viscometry methods. The characteristics were compared with commercially available gellan gum Gelzan™. The main focus of the investigation is on the rheological properties of low-molar-mass-gellan ion-induced gels and the influence of reduced molar mass on gelling of gellan. The gels were prepared by adding 0.2–0.3 M of NaCl or KCl to the 0.6 g/dL gellan gum aqueous solution in a 1:1 ratio. The kinetics of gelling at room temperature, studied by rheological methods, strongly depends on molar mass and is practically independent of the temperature (up to 37 °C) and the type of ions. Analysis of the mechanical spectra characterized the obtained gels as weak gels. The gelling temperature achieved upon cooling for low-molar-mass gellan with a 0.1 M NaCl concentration was 39.0 °C (rheology) and 43.5–42.5 °C (visual observation). In summary, this study complements the existing knowledge about how the reduced molar mass of low-acyl gellan gum influences its rheological properties and gelling behavior in ion-induced systems and provides insights into the formulation of gellan-based gels, which can be effectively utilized in various food and pharmaceutical applications. Full article

The gas–water relative-permeability relationship in tight gas is complex due to interactions between the gas and water phases within the porous media in the reservoir. To clarify the fluid occurrence and the gas–water relative-permeability behavior in such reservoirs, the Dongsheng tight water-bearing reservoir from the Ordos Basin of China is taken as the research object. A non-steady state method is employed to explore the co-permeability of gas and water phases under dynamic conditions. The irreducible water saturation of different core samples is analyzed using nuclear magnetic resonance (NMR) centrifugation. The Simplified Stone equation is applied for phase permeability normalization. The results indicate that with the decrease in core permeability, the irreducible water saturation increases, and the gas and water permeability decreases. When the displacement pressure difference increases, the gas phase permeability decreases, and the water phase permeability increases. The centrifugal method is effective in reducing the saturation of bound water in rock cores. The displacement method forms channels using gas, which effectively removes free water, particularly in larger or smaller pores. In contrast, centrifugation further displaces water from smaller or capillary pores, where flow is more restricted. Based on these experimental findings, a relationship between displacement pressure difference, critical irreducible water saturation, and residual gas saturation is established. The Stone equation is further refined, and a phase permeability normalization curve is proposed, accounting for the true irreducible water saturation of rock. This provides a more accurate theoretical framework for understanding and managing the gas–water interaction in tight gas reservoirs with a high water content, ultimately aiding in the optimization of reservoir development strategies. Full article

To investigate the pore structure evolution characteristics and damage mechanism of sandstone subjected to treatment with freeze–thaw cycles, quantitative analyses were conducted on the longitudinal wave velocity (LWV) and T₂ spectrum of sandstone before and after 10, 20, 30, and 40 freeze–thaw cycles, using longitudinal wave velocity testing, low-field nuclear magnetic resonance (NMR) testing, and fractal theory. The results show that, with the increase in the number of freeze–thaw cycles, the LWV of sandstone gradually decreases, the amplitude of the saturated T₂ spectrum gradually increases, the amplitude of the centrifugal T₂ spectrum gradually decreases, the total porosity and effective porosity increase, and the residual porosity decreases. After undergoing freeze–thaw cycles, sandstone exhibits obvious fractal characteristics in both the total porosity NMR fractal dimension and the effective porosity NMR fractal dimension, and the growth rates of both decrease exponentially with the increase in the number of freeze–thaw cycles. The magnitude of the fractal dimensions reflects the complexity of the pore structure, with smaller fractal dimensions indicating better pore connectivity. In summary, the damage evolution mechanism of sandstone under freeze–thaw cycles is characterized by the gradual expansion and interconnection of internal closed micro-pores (cracks), along with increased total porosity and effective porosity, leading to enhanced freeze–thaw damage. Full article

Introduction/Objectives: Since the biological activities and toxicities of ‘foreign’ and/or excess levels of metal ions are predominantly determined by their precise molecular nature, here we have employed high-resolution ¹H NMR analysis to explore the ‘speciation’ of paramagnetic Ni(II) ions in human saliva, a potentially rich source of biomolecular Ni(II)-complexants/chelators. These studies are of relevance to the in vivo corrosion of nickel-containing metal alloy dental prostheses (NiC-MADPs) in addition to the dietary or adverse toxicological intake of Ni(II) ions by humans. Methods: Unstimulated whole-mouth human saliva samples were obtained from n = 12 pre-fasted (≥8 h) healthy participants, and clear whole-mouth salivary supernatants (WMSSs) were obtained from these via centrifugation. Microlitre aliquots of stock aqueous Ni(II) solutions were sequentially titrated into WMSS samples via micropipette. Any possible added concentration-dependent Ni(II)-mediated pH changes therein were experimentally controlled. ¹H NMR spectra were acquired on a JEOL JNM-ECZ600R/S1 spectrometer. Results: Univariate and multivariate (MV) metabolomics and MV clustering analyses were conducted in a sequential stepwise manner in order to follow the differential effects of increasing concentrations of added Ni(II). The results acquired showed that important Ni(II)-responsive biomolecules could be clustered into distinguishable patterns on the basis of added concentration-dependent responses of their resonance intensities and line widths. At low added concentrations (71 µmol/L), low-WMSS-level N-donor amino acids (especially histidine) and amines with relatively high stability constants for this paramagnetic metal ion were the most responsive (severe resonance broadenings were observed). However, at higher Ni(II) concentrations (140–670 µmol/L), weaker carboxylate O-donor ligands such as lactate, formate, succinate, and acetate were featured as major Ni(II) ligands, a consequence of their much higher WMSS concentrations, which were sufficient for them to compete for these higher Ni(II) availabilities. From these experiments, the metabolites most affected were found to be histidine ≈ methylamines > taurine ≈ lactate ≈ succinate > formate > acetate ≈ ethanol ≈ glycine ≈ N-acetylneuraminate, although they predominantly comprised carboxylato oxygen donor ligands/chelators at the higher added Ni(II) levels. Removal of the interfering effects arising from the differential biomolecular compositions of the WMSS samples collected from different participants and those from the effects exerted by a first-order interaction effect substantially enhanced the statistical significance of the differences observed between the added Ni(II) levels. The addition of EDTA to Ni(II)-treated WMSS samples successfully reversed these resonance modifications, an observation confirming the transfer of Ni(II) from the above endogenous complexants to this exogenous chelator to form the highly stable diamagnetic octahedral [Ni(II)-EDTA] complex (K_stab = 1.0 × 10¹⁹ M⁻¹). Conclusions: The results acquired demonstrated the value of linking advanced experimental design and multivariate metabolomics/statistical analysis techniques to ¹H NMR analysis for such speciation studies. These provided valuable molecular information regarding the identities of Ni(II) complexes in human saliva, which is relevant to trace metal ion speciation and toxicology, the in vivo corrosion of NiC-MADPs, and the molecular fate of ingested Ni(II) ions in this biofluid. The carcinogenic potential of these low-molecular-mass Ni(II) complexes is discussed. Full article

This article proposes the synthesis and characterization of (triethylene glycol dimethacrylate–N,N-dihydroxyethyl-p-toluidine) TEGDMA-DHEPT self-healing microcapsules for their inclusion in dental composite formulations. The obtaining method is the in situ emulsion polymerization of the (poly urea-formaldehyde) (PUF) coatings. The microcapsules were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), high-performance liquid chromatography (HPLC), and low-field nuclear magnetic resonance (NMR) techniques. The optimal formation of uniform microcapsules is achieved at a stirring speed of 800 rpm and centrifugation is no longer necessary. HPLC demonstrates that the microcapsules formed at 800 rpm show a better control of liquid release than the heterogeneous ones obtained at a lower stirring speed. The centrifuged samples have rounded shapes, with dimensions between 80 and 800 nm, while the non-centrifuged samples are more uniform, with a spherical shape and dimensions of approximately 800 nm. Full article

The bioactive flavonoids pinostrobin (PN) and panduratin A (PA) from Boesenbergia rotunda are essential for research and therapeutic applications. This study introduces an innovative method utilizing ultrasound-assisted extraction with n-hexane pre-treatment, followed by one-step centrifugal partition chromatography (CPC) purification. Extraction efficiency was evaluated using ultra high-performance liquid chromatography (UHPLC), and the isolated compounds were characterized through ¹H-NMR and liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS), adhering to AOAC validation guidelines. Optimal extraction conditions comprised a particle size of 125 μm, a solid-to-liquid ratio of 1:30 g/mL, and a 10 min extraction time, yielding a crude extract of 6.96 ± 0.07%. Using an n-hexane/MeOH/water (5/3.4/1.6, v/v) solvent system in ascending mode, PN (2.16 mg, 98.78% purity) and PA (0.4 mg, 99.69% purity) were isolated from 67 mg of crude extract within 30 min. This streamlined approach enhances purification efficiency, allowing for faster extraction and higher purity, making it a suitable method for commercial applications. Full article

Ultrasmall silver nanoparticles (2 nm) were prepared by reduction with sodium borohydride (NaBH₄) and stabilized by the ligand glutathione (a tripeptide: glycine–cysteine–glutamic acid). NMR spectroscopy and optical spectroscopy (UV and fluorescence) revealed that these particles initially consist of silver nanoparticles and fluorescing silver nanoclusters, both stabilized by glutathione. Over time, the silver nanoclusters disappear and only the silver nanoparticles remain. Furthermore, the capping ligand glutathione eliminates hydrogen sulfide (H₂S) from the central cysteine and is released from the nanoparticle surface as tripeptide glycine–dehydroalanine–glutamic acid. Hydrogen sulfide reacts with the silver core to form silver sulfide. After four weeks in dispersion at 4 °C, this process is completed. These processes cannot be detected by transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), or differential centrifugal sedimentation (DCS) as these methods cannot resolve the mixture of nanoparticles and nanoclusters or the nature of the nanoparticle core. X-ray photoelectron spectroscopy showed the mostly oxidized state of the silver nanoparticle core, Ag(+I), both in freshly prepared and in aged silver nanoparticles. These results demonstrate that ultrasmall nanoparticles can undergo unnoticed changes that considerably affect their chemical, physical, and biological properties. In particular, freshly prepared ultrasmall silver nanoparticles are much more toxic against cells and bacteria than aged particles because of the presence of the silver clusters. Full article

In this paper, 12 sandstone samples are collected from the Taiyuan Formation in Qinshui Basin, and sample types using the T₂ spectral under LF-NMR saturation and centrifugation conditions are classified. Moreover, single and multifractal models were used to calculate fractal parameters of saturated and centrifugal T₂ spectra, and the correlation between different fractal parameters, pore structure, T_2cutoff value, and pore permeability parameters was studied. The results are as follows. (1) According to the T₂ spectrum curves under centrifugation and saturation conditions, all the samples can be divided into three types. There are significant differences in the uniform pore size distribution. However, the non-uniformity of small pore distribution in type B samples is stronger than that of other types, while heterogeneity of large pore distribution is weaker than that of different types. The centrifugal T₂ spectrum curve exhibits both single-fold and multifractal characteristics. The results of a single fractal by using a centrifugal T₂ spectrum are consistent with those of a saturated T₂ spectrum, indicating that single fractal features by using centrifugal and saturated T₂ spectra are consistent. Unlike the single fractal parameters, the correlation between the saturation and centrifugal T₂ spectrum’s multifractal parameters is weak. This suggests that the physical significance conveyed by the centrifugal T₂ spectrum’s multifractal parameters differs from that of the saturated T₂ spectrum. Full article

Deep carbonate rocks are characterized by strong heterogeneity and fracture and cavity development, which have important influence on the storage and seepage capacity of reservoirs. To comprehensively characterize the developmental characteristics of the reservoir body in the intra–platform reservoir of the fourth member of the Dengying Formation in the Anyue gas field, this study employed a multiscale pore–throat structure characterization method that combines physical property analysis, core surface observation, cast thin section observation, a nuclear magnetic resonance (NMR) test, and CT scanning analysis. The results reveal that the primary storage spaces in the intra–platform reservoirs consist of inter–crystalline pores and small cavities (<2 mm), with thick throats and fractures serving as the primary flow channels. The rock density is lower in areas where solution fractures and cavities are developed, and the fractures and cavities are generally distributed in clusters. Notably, the intra–platform reservoir of the fourth member of the Dengying Formation is characterized by low asphaltene content. The presence of fractures in fracture–cavity type cores can reduce seepage resistance in the near–fracture area and enhance the drainage efficiency of small pores, as observed in the NMR test combined with centrifugation. In the centrifugal experiments, the increase in centrifugal force had the most significant impact on drainage efficiency, with the highest efficiency being 25.82% for cavity–type cores and the lowest being 6.39% for pore–type cores. Furthermore, by integrating the results of cast thin section and NMR test, the cavity–type reservoirs were further classified into two categories: dissolved cavity storage type and dissolved pore storage type. This study clarifies the storage and seepage characteristics of dissolved–pore storage reservoirs, which are challenging to develop but have high development potential. With reasonable surface operation measures, these reservoirs can provide important support for stable production in the middle and late stages of intra–platform reservoir development. Full article

Fluid components in cores are crucial parameters in evaluating the quality of a shale reservoir in both laboratory analyses and log interpretation. In the Gulong area, shale reservoirs are characterized by a high clay content, with clay spaces hosting both oil and water phases, complicating the occurrence mechanism of fluid components, as a result, traditional research methods are no longer applicable. As an advanced technique, nuclear magnetic resonance (NMR) has been applied in oilfields to determine the specific petrophysical properties of rocks. To more accurately identify the types of fluid components, this study carried out a new, well-designed 2D NMR experiment, rock pyrolysis experiment, and quantitative oil and water detection experiment (QOWDE) to study the Gulong shale. This study measured the 2D NMR map of the original state, saturation state, centrifugal state, and pyrolysis at different temperatures, and conducted mutual verification between the QOWDE and 2D NMR pyrolysis experiments to obtain the distribution of different components of Gulong shale on the 2D NMR map. Based on the experimental results, this study developed a component identification template suitable for the Gulong area and calculated the 2D NMR porosity and saturation from it. This lays a foundation for the analysis and application of fluid components in the Gulong region and provides a new experimental basis and methodological support for porosity and saturation calculations. Full article

Ultrasmall nanoparticles (diameter 2 nm) of silver, platinum, and bimetallic nanoparticles (molar ratio of Ag:Pt 0:100; 20:80; 50:50; 70:30; 100:0), stabilized by the thiolated ligand glutathione, were prepared and characterized by transmission electron microscopy, differential centrifugal sedimentation, X-ray photoelectron spectroscopy, small-angle X-ray scattering, X-ray powder diffraction, and NMR spectroscopy in aqueous dispersion. Gold nanoparticles of the same size were prepared as control. The particles were fluorescently labeled by conjugation of the dye AlexaFluor-647 via copper-catalyzed azide-alkyne cycloaddition after converting amine groups of glutathione into azide groups. All nanoparticles were well taken up by HeLa cells. The cytotoxicity was assessed with an MTT test on HeLa cells and minimal inhibitory concentration (MIC) tests on the bacteria Escherichia coli and Staphylococcus xylosus. Notably, bimetallic AgPt nanoparticles had a higher cytotoxicity against cells and bacteria than monometallic silver nanoparticles or a physical mixture of silver and platinum nanoparticles. However, the measured release of silver ions from monometallic and bimetallic silver nanoparticles in water was very low despite the ultrasmall size and the associated high specific surface area. This is probably due to the surface protection by a dense layer of thiolated ligand glutathione. Thus, the enhanced cytotoxicity of bimetallic AgPt nanoparticles is caused by the biological environment in cell culture media, together with a polarization of silver by platinum. Full article

Freesia refracta (FR), a perennial flower of the Iris family (Iridaceae), is widely used in cosmetics despite limited scientific evidence of its skin benefits and chemical composition, particularly of FR callus extract (FCE). This study identified biologically active compounds in FCE and assessed their skin benefits, focusing on anti-aging. FR calli were cultured, extracted with water at 40 °C, and analyzed using Centrifugal Partition Chromatography (CPC), Nuclear Magnetic Resonance (NMR), and HCA, revealing key compounds, namely nicotinamide and pyroglutamic acid. FCE significantly increased collagen I production by 52% in normal and aged fibroblasts and enhanced fibroblast–collagen interaction by 37%. An in vivo study of 43 female volunteers demonstrated an 11.1% reduction in skin roughness and a 2.3-fold increase in collagen density after 28 days of cream application containing 3% FCE. Additionally, the preservation tests of cosmetics containing FCE confirmed their stability over 12 weeks. These results suggest that FCE offers substantial anti-aging benefits by enhancing collagen production and fibroblast–collagen interactions. These findings highlighted the potential of FCE in cosmetic applications, providing significant improvements in skin smoothness and overall appearance. This study fills a gap in the scientific literature regarding the skin benefits and chemical composition of FR callus extract, supporting its use in the development of effective cosmeceuticals. Full article

Controlling the extent of water invasion in the reservoir and mitigating its detrimental effects on gas well production and natural gas recovery have long been a challenging task in the efficient development of strongly heterogeneous edge water gas reservoirs. To elucidate the edge water invasion mechanism of strongly heterogeneous carbonate gas reservoirs, this study investigates the pore throat characteristics and fluid mobility from both qualitative and quantitative aspects, leveraging natural core observations, cast thin sections, scanning electron microscopy (SEM), and nuclear magnetic resonance (NMR) tests with centrifuge experiments. A core-scale edge water invasion simulation experiment was conducted under online NMR monitoring to examine the dynamic gas production characteristics of the three types of reservoirs during the water invasion process and to elucidate the formation mechanism and distribution pattern of water-sealed gas. Research findings indicate that carbonate reservoirs typically exhibit a diverse range of pore types, including various types of fractures and cavities. Fractures significantly enhance reservoir connectivity, thereby increasing fluid mobility, but also lead to strong non-uniform water invasion. In contrast, cavities substantially improve the storage capacity of the reservoir and can retard the advancement of the water invasion front, thereby alleviating the adverse effects of water invasion. The ultimate recovery rates of fracture-type, cavity-type, and fracture-cavity cores in the water invasion simulation experiment were 29.81%, 64.87%, and 53.03%, respectively. Premature water breakthroughs in the reservoir can result in a large number of gases in matrix pores and even cavities being sealed by formation water, rendering them unrecoverable, which seriously impacts the gas recovery rate of the reservoir. Full article