Journal of Chromatography A最新文献

The ability of reduced graphene oxide aerogels (rGOAs) for challenging gas-phase separation was investigated with hexane isomers and benzene (C6 hydrocarbons) using inverse gas chromatography (IGC). For the first, rGOAs were synthesized with sodium dithionite (DTN) as a reductant. Experiments revealed that the most optimal DTN to graphene oxide mass ratio was 2:1, resulting in the highest specific surface area of 432.3 m² g⁻¹ and the highest degree of graphitization among analyzed samples. C6 hydrocarbon adsorption tests demonstrated the dominant role of the kinetic effect for the adsorption of branched and cyclic hexane isomers - the partition coefficient decreased as the molecule kinetic diameter increased. The contribution of thermodynamic effects was distinguished for molecules with uneven charge distribution. A comparison of the partition coefficient ratios for different pairs of hydrocarbons demonstrated the potential of rGOAs in separating various C6 hydrocarbons. The selectivity, calculated from binary-component adsorption tests of benzene (Bz)/cC6 equimolar mixture, was 13.7, 8.5 and 2.8 for DTN4, DTN2, and DTN1. The research indicates that rGOAs may have potential as adsorbents for the selective separation of hydrocarbons, however, the competitive adsorption and performance at high surface coverages of adsorbates have to be accounted for in further research to assess the applicability of rGOAs reliably.

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) are pervasive contaminants in aquatic environments. They are characterized by persistence, toxicity, bioaccumulation, and long-range transport, significantly threatening human health. The development of sensitive methods for nitro-PAH analysis in environmental samples is in great need. This study developed a novel carbonaceous SPME coating derived from metal-organic framework (MOF), namely a spherical assembly consisting of carbon nanorods with hierarchical porosity (HP-MOF-C), for the extraction and determination of nitro-PAHs in waters. The HP-MOF-C coated fiber demonstrated superior nitro-PAH extraction efficiencies, with enrichment factors 2∼70 times higher than commercial fibers. This enhancement was due to the strong hydrophobic, π-π electron coupling/stacking, and π-π electron donor-acceptor interactions between the carbonaceous framework of HP-MOF-C and the nitro-PAHs. Moreover, the unique hierarchical porous structure of HP-MOF-C accelerated the diffusion of nitro-PAHs, further facilitating their enrichment. The fiber also exhibited good thermal stability, remarkable chemical stabilities against common acid, base, and polar/non-polar solvents, and long service life (> 150 SPME cycles). The nitro-PAH determination method based on HP-MOF-C coating yielded wide linear ranges, low detection limits (0.4∼5.0 ng L^-1), satisfactory repeatability and reproducibility, and good recoveries in real water samples. The proposed method was considered to be green according to the Analytical GREEnness assessment. The present study not only offers an efficient SPME coating for the enrichment of nitro-PAHs, but also provides insights into the design of porous coating materials.

To deal with complicated separation situations, this study successfully prepared two mixed-mode chromatography (MMC) stationary phases, CCL-SIL and PCL-SIL, by functionalizing dialdehyde cellulose (DAC) derivatives. In liquid chromatography applications, CCL-SIL exhibited superior separation performance for nucleosides and bases in HILIC mode, while PCL-SIL performed better in RPLC and IEC modes. Their distinct separation mechanisms were also elucidated by quantum chemical calculations. Both CCL-SIL and PCL-SIL showed good stability and reproducibility, with relative standard deviations of retention time, peak area, and peak height below 7.79 % and 4.37 % for multiple injections. Particularly, the PCL-SIL column and the CCL-SIL column were successfully used for the quantitative analysis of trace targets in real samples with complex matrix, demonstrating high accuracy and precision.

Ostreopsis cf. ovata, a benthic/epiphytic marine dinoflagellate, is currently spreading in tropical, sub-tropical and temperate areas, causing periodic Harmful Algal Blooms (HABs). It produces a wide array of palytoxin-like compounds named ovatoxins (OVTXs), with OVTX-a generally the most abundant congener. Despite numerous cases of human poisonings and environmental damage associated with the presence of OVTXs and O. cf. ovata proliferations, a complete characterization of the toxicity of this class of molecules cannot be performed until Reference Material (RM) for individual congeners is available. This, in turn, requires the availability of sufficient amounts of toxin at a high purity grade. To achieve this goal, herein an analytical re-evaluation of critical-steps of OVTX-a isolation from O. cf. ovata cell pellets is reported. The overall procedure consists of four steps, namely an extraction, a Medium Pressure Liquid Chromatography (MPLC) separation, and two preparative High Performance Liquid Chromatography (HPLC) steps. Particular attention was paid to the extraction step to evaluate the repeatability in OVTX-a yields. For subsequent steps, loading sample preparation and chromatographic conditions were refined. As a result, a significant increase in recovery yields (from 12.5 to 20 ± 3%) and in purity grade (from 51% to 94%) of the isolated OVTX-a was achieved in comparison to previous studies. The improved procedure can easily be applied to isolate sufficient quantities of a good candidate RM for OVTX-a.

Background

The increasing use of plastic packaging materials generates concerns related to the environmental problem generated by their waste. As a result, the search for new recycling methodologies to extend the lifecycle of plastic packaging is becoming more important, without forgetting to ensure the safety of these materials. Currently, the use of recycled polyolefins as food contact materials is not widespread yet. This is because the decontamination processes currently available are insufficient to produce clean, safe materials suitable for such applications. This work is focused on the evaluation of the safety of recycled high-density polyethylene (rHDPE), and the search for strategies to achieve its decontamination.

Results

To this end, three batches of flakes and three batches of pellets of rHDPE coming from the mechanical recycling of post-consumer milk bottles were analyzed. The analysis of the volatile and semi-volatile compounds present in the samples was carried out using gas chromatography-mass spectrometry (GC–MS), finding a total of 67 compounds. The strategy to achieve the decontamination of flakes and pellets of this material has been based on the application of high temperature and vacuum at lab scale, obtaining a clear decrease in volatile compounds, below 50% of the initial value in most cases when applying 120 °C during 5 h. The migration test performed in the samples (treated and untreated) to different food simulants (10 % ethanol and 3 % acetic acid, 95 % ethanol) revealed also a clear decrease of concentrations of volatiles.

Significance

The findings are highly encouraging, demonstrating substantial progress toward the safe and effective use of rHDPE in specific food packaging applications. This indicates a significant step forward in the potential uses of rHDPE. Nevertheless, the lack of toxicity data for many migrants necessitates additional toxicological testing to obtain a more precise risk assessment.

A novel nanofibrous double-layered biosorbent was fabricated by electrospinning polyethersulfone (PES) doped with a natural deep eutectic solvent (DES), composed of choline chloride (ChCl) and caffeic acid (CFA) in a 3:1 molar ratio, onto a bacterial cellulose (BC) substrate. The pristine PES/DES@BC biosorbent was employed in a thin film-solid phase microextraction (TF-SPME) to extract 12 multiclass pesticides from water. Characterization techniques, including ATR-FTIR, FT-NMR, SEM, and nitrogen adsorption/desorption isotherms, confirmed the nanofibrous structure of the electrospun PES-DES and BC biopolymer. The method was validated for matrix effect, specificity, reproducibility, limits of quantification (0.03–0.10 µg/L), and enrichment factor (7–14). Matrix-match calibration linearity ranged from 0.03 to 500 μg/L, with determination coefficients (r²) between 0.9884 and 0.9994. Intra-day and inter-day relative standard deviations (RSDs) were 1.2–3.6 % and 7.0–9.3 %, respectively. The composition of the biosorbent and the fabrication reproducibility across different batches were also thoroughly examined. The accuracy was evaluated by measuring extraction recoveries in six environmental water samples, which ranged from 75 to 105 % (RSDs < 9.0 %). Furthermore, the sustainability of the method was evaluated with the Analytical Eco-Scale and Analytical Greenness metrics. To our knowledge, this study represents the first synthesis and combination of [ChCl:[CFA] DES with PES to create a double-layered nanofiber biosorbent, as well as its application for extracting various pesticide groups from water samples.

The Soret effect is a significant factor in various scenarios, with thermodiffusion in binary systems serving as a common method for the study. Most research focuses rarely on the distribution characteristics of components in diffusion systems; and Soret coefficients in the porous media could not be obtained by typical methods based on the thermodiffusion column, which are particularly important in the field of oil and gas development. Moreover, experiments on ground conditions have struggled to determine the Soret coefficient accurately due to the convective effect caused by gravity differentiation. The thermodiffusion behavior of n-pentane (C5) and n-heptane (C7) binary mixtures in both bulk and porous media conditions have been investigated, aiming to provide corrected coefficients that mitigate the influence of gravity using theoretical derivation. A new method was proposed to calculate the Soret coefficients in this work by establishing a model based on gas chromatography technology. Dynamic variation of component concentration along the path was studied, and the corresponding Soret coefficients were calculated and analyzed in parallel. The results indicate that the concentration and temperature exhibit a logarithmic relationship with the distance from the heat source. The Soret coefficient values obtained from measurements in porous media are closer to the theoretically corrected values, which do not account for gravity effects. Additionally, as the permeability decreases, the counteracting effect of porous media on convection becomes more pronounced. Therefore, it presents a novel method for accurately measuring the Soret coefficient that ignores convection to some extent.

Metal–organic frameworks (MOFs) are promising materials for sample pretreatment. The performance improvement of powdered MOFs is hindered by their aggregation and difficult recovery. To overcome these issues, a biodegradable lightweight spherical aerogel was used as a support for the in situ growth of copper-based MOFs (MOF-199). Furthermore, Fe₃O₄ nanoparticles were incorporated into the aerogel to achieve magnetic properties. Thus, hybrid aerogel spheres containing MOF-199 supported on magnetic oxidized cellulose nanofiber/carboxymethyl chitosan (MOF-199@mag-CNF/CMC) were fabricated. The effects of Fe₃O₄ loading amount and organic-ligand concentration on the properties (spherical geometry and mechanical strength) of the hybrid aerogel spheres were studied. Their potential application in the extraction of benzodiazepines (BZPs) from urine samples prior to liquid chromatography–mass spectrometry was evaluated. The highly dispersed MOF-199 crystals on the spherical aerogel effectively overcame the inherent structural shrinkage of the bare aerogel spheres; thus, the MOF-199@mag-CNF/CMC aerogel spheres were robust and could withstand repeated use for at least eight consecutive extraction cycles. Further, MOF-199@mag-CNF/CMC exhibited improved BZP extraction efficiency, which was 2.5–11.6 times higher than that of bare Cu²⁺@mag-CNF/CMC aerogel spheres, primarily due to additional π–π interaction and H-bonding as well as improved specific surface area. Parameters influencing the extraction and desorption processes were also comprehensively investigated. Under optimal conditions, this method provided a wide linear range of 0.1–10 µg/L (R² > 0.995) and good precision (2.8–6.7% for intra-day; 1.9–7.8 % for inter-day). The limits of detection and quantification ranged from 0.02 to 0.11 µg/L and from 0.06 to 0.33 µg/L, respectively. The recoveries for the urine samples spiked with three concentrations of BZPs ranged from 73.9 % to 114.1 %. The proposed method is simple, sensitive and eco-friendly and can be used for the determination of BZPs from urine for clinical and forensic examinations.

Simultaneous separation of compounds with multiple chiral centers and highly similar structures presents significant challenges. This study developed a novel supercritical fluid chromatography (SFC) method with reduced organic solvent consumption and robust separation capabilities to address these challenges. The method was applied to simultaneously achieve enantioselective, diastereoselective, and achiral separation of palonosetron hydrochloride and its six impurities. The effects of the polysaccharide-based chiral stationary phase (CSP), modifier, additive, and column temperature on retention and separation were comprehensively evaluated. It was found that a combination of a polysaccharide-based CSP and a single modifier or a mixture of protonic modifiers could not achieve complete separation due to high structural similarity. However, an ADH column and a ternary solvent mixture containing acetonitrile (methanol: acetonitrile: diethylamine, 60:40:0.2, v/v/v) provided satisfying separation, particularly for the enantiomer and diastereomers of palonosetron. Using the optimized method, the enantioselective, diastereoselective, and achiral separation of palonosetron hydrochloride and its six impurities can be accomplished in 18 min under gradient elution. Thermodynamic results indicated that the separation process was entropy driven. A molecular docking study revealed that the separation was mainly achieved through the differences in hydrogen bond and π - π interactions between the analytes and CSP. This study lays the foundation for SFC analysis of palonosetron hydrochloride and provides a reference for the simultaneous SFC separation of the enantiomers, diastereoisomers and structurally similar compounds.

In the field of nuclear toxicology, the knowledge of the interaction of actinides (An) with biomolecules is of prime concern in order to elucidate their toxicity mechanism and to further develop selective decorporating agents. In this work, we demonstrated the great potential of hydrophilic interaction liquid chromatography (HILIC) to separate polar thorium (Th) biomimetic peptide complexes, as a key starting point to tackle these challenges. Th⁴⁺ was used as plutonium (Pu⁴⁺) analogue and pS16 and pS1368 as synthetic di- and tetra-phosphorylated peptides capable of mimicking the interaction sites of these An in osteopontin (OPN), a hyperphosphorylated protein. The objective was to determine the relative affinity of pS16 and pS1368 towards Th⁴⁺, and to evaluate the pS1368 selectivity when Th⁴⁺ was in competition complexation reaction with UO₂²⁺ at physiological pH. To meet these aims, HILIC was simultaneously coupled to electrospray ionization mass spectrometry (ESI-MS) and inductively coupled plasma mass spectrometry (ICP-MS), which allowed to identify online the molecular structure of the separated complexes and quantify them, in a single step. Dedicated HILIC conditions were firstly set up to separate the new dimeric Th₂(peptide)₂ complexes with good separation resolution (peptide = pS16 or pS1368). By adding pS16 and pS1368 in different proportions relatively to Th⁴⁺, we found that lower or equal proportions of pS16 with respect to pS1368 were not sufficient to displace pS1368 from Th₂pS1368₂ and pS16 proportion higher than pS1368 led to the formation of a predominant ternary complex Th₂(pS16)(pS1368), demonstrating preferential Th⁴⁺ binding to the tetra-phosphorylated peptide. Finally, online identification and quantification of the formed complexes when Th⁴⁺ and UO₂²⁺ were mixed in equimolar ratio relatively to pS1368 showed that in spite of pS1368 has been specifically designed to coordinate UO₂²⁺, pS1368 is also Th⁴⁺-selective and exhibits stronger affinity for this latter than for UO₂²⁺. Hence, the results gathered through this approach highlight the impact of Th⁴⁺ coordination chemistry on its interaction with pS1368 and more widely to its affinity for biomolecules.