Search Results (48)

Background: Phospholipids are essential components of bacterial membranes and play central roles in membrane integrity and adaptation to antibiotic stress. However, confident annotation of phospholipid molecular species remains challenging due to the complexity of the lipidome and the limited structural constraints in conventional lipidomics workflows. Methods: Here, we present a bacterial phospholipidomic framework that integrates orthogonal structural evidence to achieve high-confidence and traceable annotation. Thin-layer chromatography (TLC) provides phospholipid headgroup assignment, gas chromatography–mass spectrometry (GC–MS) defines the acyl-chain pool, and Paternò–Büchi derivatization enables C=C localization, collectively restricting the structural search space prior to liquid chromatography–tandem mass spectrometry (LC–MS/MS) analysis. A rule-based ion prediction library further standardizes diagnostic ion assignment and reduces annotation ambiguity. Results: Applying this platform, we found Escherichia coli in the stationary phase remodeled the membrane phospholipids, with cardiolipin (CL) increasing from ~5% to ~10% and cyclopropane-containing phospholipid species rising to ~75%. Similar remodeling patterns are observed under diverse antibiotic exposures at sub-inhibitory concentrations, consistent with convergence toward a tolerance-associated membrane state. Extension of the framework to Enterococcus faecium supports proof-of-concept application in an additional Gram-positive model, with vancomycin-resistant strains exhibiting pronounced phosphatidylglycerol (PG) enrichment and reduced CL. Conclusions: Our work provides a scalable and reproducible strategy for bacterial phospholipid annotation, enabling molecular-species-resolved investigation of membrane adaptation and offering a framework for future exploration of lipid homeostasis pathways as potential antimicrobial targets. Full article

Lithium iron phosphate (LiFePO₄) (LFP) has emerged as the most popular cathode material in the current lithium battery market because of its stable charge–discharge cycle performance, low cost, and high safety. Moreover, this material does not require scarce resources such as nickel and cobalt, which alleviates supply chain conflicts and reduces the environmental and health impacts associated with Ni and Co. In this study, a cost-effective preparation method is implemented to synthesize a series of all-element integrated LiFePO₄ precursors using precursor solutions with varying concentrations of oxalic acid. The final LFP materials are subsequently obtained through a one-step heat treatment. To evaluate the advantages of this method, we compare the structural and electrochemical properties of the obtained LFP materials with those synthesized via the traditional solid-phase method. The experimental results reveal that the LFP material synthesized using an oxalic acid solution with a concentration of 0.125 mol L⁻¹ exhibits optimal performance. This material has a grain size in the range of 300–500 nm, which is smaller and more uniform than those of the other samples. This initial specific discharge capacity of the designed LFP is 150.3 mAh·g⁻¹, with an initial coulombic efficiency of 88%. Notably, the material maintains a high capacity of 98 mAh·g⁻¹ even at −20 °C and achieves a discharge capacity of 98.7 mAh·g⁻¹ at a high discharge rate of 5 C. The lithium-ion diffusion coefficient was determined to be 7.1 × 10⁻¹² cm² s⁻¹, which is approximately 2.5 times greater than that of the material synthesized via the solid-phase ball-milling method. These results highlight the significant improvements in both the structural and electrochemical properties of LFP materials synthesized through this novel liquid-phase method. Full article

In this study, an ion-pair reverse-phase high-performance liquid chromatography–electrospray ionization mass spectrometry (RP-HPLC-ESI-MS) method was optimized and validated for purity determination for the quality control of the proposed generic nusinersen oligonucleotide drug substance and drug product. The optimization and considerations of sample preparation, chromatographic and mass spectrometry conditions are discussed. The limit of detection was 2.5 × 10⁻⁵ mg/mL and the limit of quantitation was 4.9 × 10⁻⁵ mg/mL. The linearity of the signal (XIC) for all impurities was linear with correlation coefficients of R² ≥ 0.9669. This study, associated with the development of therapeutic oligonucleotides, examines the subject of product-related impurities. The authors consider an ion-pair reverse-phase high-performance liquid chromatography in combination with mass spectrometry for impurity quantitative control. This study contributes to the field by elucidating several critical aspects that, while previously unaddressed in the existing literature, are essential for developing effective analytical methods. Full article

The electrodeposition of rare earth metal alloys has attracted considerable interest, not only due to the challenges associated with the reduction in metal ions, but also because of their unique material properties and promising technological applications. This review presents a comprehensive analysis of the state-of-the-art in the electrochemical deposition of these alloys, focusing on various electrolytic systems, including aqueous solutions, organic molecular solvents, ionic liquids, and deep eutectic solvents. Despite inherent problematic factors such as low reduction potentials, competing hydrogen evolution reactions, and difficulties in controlling metal formation, recent advancements have enabled improved control over film formation, typically through the induced codeposition of lanthanides with iron-group metals. The influence of key factors, such as electrolyte composition and current/potential modes, on alloy codeposition, elemental and phase composition, structure, and deposition efficiency is discussed. The magnetic properties, electrocatalytic behavior, and corrosion resistance of the deposited films are also shown, highlighting their relevance for high-performance applications. Full article

Per- and polyfluoroalkyl substances (PFAS) are synthetics prized for their chemical stability and functionality. Legacy PFAS such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have been phased out due to their persistence and toxicity. This study assessed exposure to both legacy and emerging PFAS in 281 urine samples from 8-year-old children participating in the (Infancia y Medio Ambiente) INMA Asturias birth cohort (northwest Spain), a region with a strong industrial background. Dietary and household information was collected via questionnaires, and urine samples were analysed using ultra-high-performance liquid chromatography (UHPLC) coupled with high-resolution mass spectrometry (HRMS) with full-scan acquisition in independent all-ion fragmentation mode. A suspected screening approach was applied to discover previously unreported PFAS and expand the detectable chemical profile, complemented by targeted analysis of 29 compounds selected for their persistence and regulatory relevance. Among them, 17 compounds were confirmed and quantified. The combined targeted and suspect-screening approach also identified novel PFAS, including fluorotelomer carboxylic acids, demonstrating the value of LC-HRMS for detecting unregulated compounds. Emerging PFAS showed the highest detection frequencies and concentrations: trifluoroacetic acid (TFA) and hexafluoropropylene oxide dimer acid (HFPO-DA, GenX) were detected in 63% and 27% of samples, respectively, with GenX reaching 10.1 ng/mL, whereas PFOA and PFOS were detected less frequently (8.5% and 3.2%) and at concentrations below 1 ng/mL, highlighting the need for epidemiological studies to achieve comprehensive PFAS exposure assessments. Associations with dietary habit exposure estimates point to dairy, protein-rich foods, vegetables, and drinking water as the main contributors. Full article

Best known as an organizer of the mitotic spindle, the protein product of the human assembly factor for spindle microtubules (ASPM) gene has recently been shown to function in the interphase nucleus during multiple DNA-associated processes, including BRCA1-mediated DNA DSB repair, ATR-CHK1 activation during replication stress, and transcription regulation alongside the transcription factor FOXM1. In this review, we provide an overview of these DNA-related roles of ASPM. Additionally, we suggest the facilitation of liquid–liquid phase separation (LLPS) as a potential unifying mechanism underlying ASPM function. We also consider the implications of LLPS and ASPM dysfunction in disease, and highlight the impact of cellular context including cell cycle phase-dependent post-translational protein modifications and ion concentrations. An increased understanding of LLPS in ASPM function relevant to genome stability may enable future drug discovery for diseases such as cancer. Full article

In the context of the current global transition toward low-carbon energy, the issue of $C{O}_2$ utilization has become increasingly important. One of the most promising natural targets for $C{O}_2$ sequestration is the terrigenous sedimentary formations found in oil, gas, and coal basins. It is generally assumed that $C{O}_2$ injected into such formations can be stored indefinitely in a stable form. However, the dissolution of $C{O}_2$ into subsurface water leads to a reduction in pH, which may cause partial dissolution of the host formation, altering the structure of the subsurface in the injection zone. This process is relatively slow, potentially unfolding over decades or even centuries, and its long-term consequences require careful investigation through mathematical modeling. The geological formation is treated as a partially soluble porous medium, where the dissolution rate is governed by surface chemical reactions occurring at the pore boundaries. In this study, we present an applied mathematical model that captures the coupled processes of mass transport, surface chemical reactions, and the resulting microscopic changes in the pore structure of the formation. To ensure the model remains grounded in realistic geological conditions, we based it on exploration data characterizing the composition and microstructure of the pore space typical of the Cenomanian suite in northern Western Siberia. The model incorporates the dominant geochemical reactions involving calcium carbonate (calcite, $CaC{O}_3$), characteristic of Cenomanian reservoir rocks. It describes the dissolution of $C{O}_2$ in the pore fluid and the associated evolution of ion concentrations, specifically $H^{+}$, $C{a}^{2+}$, and $HC{O}_3^{-}$. The input parameters are derived from experimental data. While the model focuses on calcite-based formations, the algorithm can be adapted to other mineralogies with appropriate modifications to the reaction terms. The simulation domain is defined as a cubic region with a side length of 1 $\mathsf{\mu }$m, representing a fragment of the geological formation with a porosity of 0.33. The pore space is initially filled with a mixture of liquid $C{O}_2$ and water at known saturation levels. The mathematical framework consists of a system of diffusion–reaction equations describing the dissolution of $C{O}_2$ in water and the subsequent mineral dissolution, coupled with a model for surface evolution of the solid phase. This model enables calculation of surface reaction rates within the porous medium and estimates the timescales over which significant changes in pore structure may occur, depending on the relative saturations of water and liquid $C{O}_2$. Full article

A novel centrifuge-less cloud point extraction (CL-CPE) method was developed for the spectrophotometric determination of copper(II) using 4-nitrocatechol (4NC) as the chelating agent. The extraction system utilizes a mixed micellar phase composed of the nonionic surfactant Triton X-114 and the ionic liquid (IL) Aliquat^® 336 (A336). The extracted ternary ion-association complex, identified as (A336⁺)₂[Cu(4NC)₂], exhibits a maximum absorbance at 451 nm, with a molar absorption coefficient of 8.9 × 10⁴ M⁻¹ cm⁻¹ and a Sandell’s sensitivity of 0.71 ng cm⁻². The method demonstrates a linear response in the copper(II) concentration range of 32–763 ng mL⁻¹ and a limit of detection of 9.7 ng mL⁻¹. The logarithmic extraction constant (log K_ex) was determined to be 7.9, indicating efficient extraction. Method performance, evaluated by the Blue Applicability Grade Index (BAGI) and the Click Analytical Chemistry Index (CACI), confirmed its feasibility, practicality, simplicity, convenience, cost-effectiveness, environmental friendliness, and analytical competitiveness. The proposed IL-CL-CPE method was successfully applied to the analysis of a dietary supplement, a solution for infusion, and synthetic mixtures simulating various copper alloys. Full article

Stable isotope analysis is a powerful tool for inferring and quantifying transformation processes, but its effectiveness relies on understanding the magnitude and variability of isotopic fractionation associated with specific reactions. Potassium permanganate (KMnO₄) is widely used as an efficient oxidant for the degradation of trichloroethylene (TCE); however, the influence of environmental factors on the isotope fractionation during this process remains unclear. In this study, compound-specific isotope analysis (CSIA) was conducted to investigate the variability in carbon isotope effects during the KMnO₄-mediated degradation of TCE under varying conditions, including initial concentrations of KMnO₄ and TCE, the presence of humic acid (HA), pH levels, and inorganic ions. The results showed that the overall carbon isotope enrichment factors (ε) of TCE ranged from −26.5 ± 0.5‰ to −22.8 ± 0.9‰, indicating relatively small variations across conditions. At low KMnO₄/TCE molar ratio (n(KMnO₄)/n(TCE)), incomplete oxidation and/or MnO₂-mediated oxidation of TCE likely resulted in smaller ε. For dense, non-aqueous phase liquid (DNAPL) TCE, which represents extremely high concentrations, the ε value was −13.0 ± 1.7‰ during KMnO₄ oxidation. This may be attributed to the slow dissolution of isotopically light TCE from the DNAPL phase, altering the δ¹³C signature of the reacted TCE and resulting in a significantly larger ε value than observed for dissolved-phase TCE oxidation. The ε values increased with rising pH, probably due to the decrease in oxidation potential (E₀) of KMnO₄ from pH ~2 to ~12, as well as the emergence of different degradation pathways and intermediates under varying pH conditions. Both SO₄²⁻ and NO₃⁻ slightly influenced the ε values, potentially due to the formation of H₂SO₄ and HNO₃ at lower pH, which may act as auxiliary oxidants and contribute to TCE degradation. A high concentration (50 mM) of HA led to a decrease in ε values, likely due to competitive interactions between HA and TCE for KMnO₄, which reduced the effective oxidation of TCE. Overall, the carbon isotope enrichment factors for KMnO₄-mediated TCE degradation are relatively stable, although certain environmental conditions can exert minor influences. These findings highlight the need for caution when applying quantitative assessment based on CSIA for KMnO₄ oxidation of TCE. Full article

Previous coreflooding results and wettability analyses in our group show that injection of naphthenic-acid-enriched water can improve oil recovery over traditional waterflooding. This observation is still a subject of research efforts without a definitive explanation. Naphthenic acids (NA) have been reported to drive wettability alteration and increase the water–oil interface elasticity. These alterations depend on the NA carbon number and aqueous-phase salinity, among other conditions, as reported in the literature. Smart-water flooding (SWF) research often links recovery to the initial wettability condition, being higher for initially oil-wet rock. SWF refers to a technique in which the aqueous-phase ion composition or/and salinity are changed to maximize oil recovery. Given NAs’ complex solution behavior, selecting acid combinations that prompt oil recovery is a difficult objective. The aim of this research is to determine the effects of select naphthenic acids on the oil–water interfacial rheology and wettability alteration and how these interfacial effects are associated with oil recovery under spontaneous imbibition. NAs were selected based on their carbon number, molecular structure, and solubility in the saline solution used in this research. We aimed at exploring which NAs should be used to regulate interfacial properties so as to either increase oil recovery or accelerate production. Time-domain nuclear magnetic resonance, interfacial dilatational rheology, and liquid-bridge experiments, i.e., proxy of snap-off, were conducted. A baseline was established using results obtained with a previously tested sulfate-rich aqueous phase, shown to be effective in recovering oil. Results show that NA14 and N18 increase the water–oil interfacial viscoelasticity and induce interfacial healing but led to different recovery factors. N10, while effective at inducing water wetness in oil-wet rock, is ineffective at increasing the recovery factor. We concluded that wettability and oil–water interfacial rheology are not exclusive, and instead they can synergistically favor EOR benefits. Moreover, oil recovery benefits under spontaneous imbibition are shown to depend strongly on the initial wettability conditions. Full article

A novel design for vortex-assisted liquid–liquid microextraction (VALLME), combined with spectrofluorimetric determination (FLD), was proposed and successfully tested for determining picric acid (PA) in water samples. This fluorescence method is based on the formation of an ion associate (IA) through electrostatic interactions, which serves as the analytical species for fluorescence measurement in the presence of the basic polymethine dye Astrafloksin (AF). The approach aims to minimize the volume of the extraction phase, aligning with the principles of green analytical chemistry. The calibration curve was linear from 0.92 to 11.45 µg L⁻¹, with an R² of 0.9930. LOD was 0.40 µg L⁻¹. Density functional theory (DFT) calculations, supported by analysis of van der Waals and electrostatic interionic attraction, helped explain the experimentally observed selectivity of the AF cation for picrate compared to other selected phenols. Theoretical solubility descriptors of the proposed IA provided insight into the extraction of IA from water to the n-amyl acetate phase. This VALLME-FLD method represents a significant advancement in PA determination, characterized by high sensitivity, selectivity, and procedural simplicity. It minimizes the use of organic solvents, facilitates direct sample preparation, and shortens analysis time. The developed method was successfully applied to real samples. Full article

The consumption of grape seed extracts is known for its contribution to animal and human health and is associated with its relevant procyanidin content. However, there is a little scientific unanimity whether these properties are due to the procyanidin content or to the length of their polymers. The main reason for this doubt is the technical difficulties related to their separation. Therefore, a preparative separation of grape seed extract was carried out using an integrated ultra/diafiltration procedure with membranes of 300, 30, 5, and 1 kDa molecular mass cut-offs, reverse osmosis and solid-phase extraction to obtain fractions of very high (>300 kDa), high (300–30 kDa), intermediate (30–5 kDa), low molecular mass (5–1 kDa), very-low-mass polar molecules and ions (<1 kDa), and very-low-mass dipole molecules (<1 kDa). Process parameters, mass transfer across the membranes and the quality of separation of each fraction are described and discussed in depth. A high degree of purification was achieved for the higher-molecular-mass fractions (>300, 300–30, and 30–5 kDa), as well as the big majority of procyanidin polymers and oligomers from very-low-molecular-mass species. All fractions were characterized for their procyanidin content by normal phase high-performance liquid chromatography coupled to a photodiode array detector (NP-HPLC-PAD). This analytical technique has shown for the first time that not only do oligomeric procyanidins elute at an increasing order of elution, but polymeric ones also do the same. Full article

We discovered that the radical cation salt [1^•+][NTf₂⁻], composed of tetrakis(ethylthio)tetrathiafulvalene radical cation and bis(N-trifluoromethanesulfonyl)imide ion, exhibits significant changes in its magnetic properties during a solid–liquid phase transition. Single-crystal structure analysis revealed that the radical cation salt [1^•+][NTf₂⁻] forms an associated structure called a π-dimer in the crystalline phase. The extremely weak ESR signal in the crystalline state indicates strong antiferromagnetic interactions between unpaired electrons within the π-dimer. Upon heating, the crystalline phase transitions into a liquid state without decomposition at 144 °C (417 K). The ESR signals in the liquid state are significantly stronger than those in the solid state, suggesting the formation of a paramagnetic state with weak interactions between radical cations. Full article

Nitrite is a health and environmental hazard and pollutes water sources globally, but sensitive, rapid, and facile quantification methods are lacking. Herein, we report a method for extracting and quantifying low-concentration nitrite in surface water using minimal sample and solvent volumes. The nitrite reacted with sulfanilamide and N-1-naphthylethylenediammonium dichloride (NED), yielding an azo dye for extraction into an organic ion-associate liquid phase (IALP) formed in situ using ethylhexyloxypropylammonium and dodecyl sulfate ions. The addition of sodium acetate increased the pH, decreasing the cation charge from +2 to +1, improving extraction efficiency. Further, adding NaCl doubled the IALP volume, reduced the required standing time, and minimally affected absorbance, and adding concentrated HCl to the IALP enhanced the absorbance intensity via dye protonation. Crucially, the method achieved a 30-fold concentration factor compared to traditional pre-treatment methods, even without centrifugation, as well as a limit of detection of 0.09 µg NO₂-N/L. Spiked recovery tests with river and seawater samples (93–103%) matched those of established methods. Digital imaging of IALP-extracted lake water yielded a limit of detection of 0.4 µg NO₂-N/L. The method is a sensitive, efficient approach for nitrite detection, enabling rapid environmental monitoring via spectrophotometry and digital imaging. Full article

In this study, we present a method for ion-associated liquid phase (IALP) separation and concentration of analytes from an aqueous matrix into an IALP formed in situ by the charge neutralization reaction of organic cations and anions, without centrifugation. The effects of various factors on the extraction efficiency and other parameters are investigated, whereas no instrumental stirring, such as vortexing or ultrasonics, is required because the solvent (IALP) is formed in situ. The organic cation and anion used are ethylhexyloxypropylammonium and dodecyl sulfate, respectively. The developed in situ IALP microextraction method for phase separation without centrifugation is tested using the thymol blue dye and several endocrine disruptors. The tested endocrine disruptors (bisphenol A, 17β-estradiol, 17α-ethinylestradiol, and estrone) are analyzed via high-performance liquid chromatography/fluorescence detection, with respective detection limits of 0.02, 0.02, 0.02, and 0.4 μg L⁻¹, and the corresponding enrichment factor ranging from 47 to 71. This IALP microextraction method can be used to separate and concentrate environmental water samples of different matrices. The employed IALP is fast and easy to use, enables an approximately 100-fold analyte concentration, and has a high affinity for estrogens, thus holding promise for the separation, concentration, and quantitation of diverse trace analytes. Full article