Separations, Volume 8, Issue 4 (April 2021) – 19 articles

Hydrophilic interaction liquid chromatography (HILIC) is able to separate from polar to highly polar solutes, using similar eluents to those in the reversed-phase mode (RPLC) and a polar stationary phase, where water is adsorbed onto its surface. It is widely accepted that multiple modes of interaction take place in the HILIC environment, which can be far more complex than the interactions in an RPLC column. The behaviour in HILIC should be adequately modelled to predict the retention with optimisation purposes and improve the understanding on retention mechanisms, as is the case for RPLC. In this work, the prediction performance of several retention models is studied for seven HILIC columns (underivatised silica, and silica containing diol, amino and sulfobetaine functional groups, together with three columns recently manufactured with neutral, anionic, and cationic character), using uracil and six polar nucleosides (adenosine, cytidine, guanosine, thymidine, uridine, and xanthosine) as probe compounds. The results in HILIC are compared with those that were offered by the elution of several polar sulphonamides and diuretics analysed with two C18 columns (Chromolith Speed ROD and Zorbax Eclipse XDB). It is shown that eight retention models, which only consider partitioning or both partitioning and adsorption, give similar good accuracy in predictions for both HILIC and RPLC columns. However, the study on the elution strength behaviour, at varying mobile phase composition, reveals similarities (or differences) between RPLC and HILIC columns of diverse nature. The particular behaviour for the HILIC and RPLC columns was also revealed when the retention, in both modes, was fitted to a model that describes the change in the elution strength with the modifier concentration. Full article

The benefits of ginseng have been mainly attributed to its triterpenoids, called ginsenosides. Recent genome sequencing of the Panax ginseng has paved the way for in-depth proteomic studies of this medicinal plant. The current study was conducted to deepen the proteomic information on the root proteome of Korean ginseng. Proteomic workflow was optimized by testing two different strategies, characterized by the phenol extraction procedure, the presence or the absence of SDS-PAGE fractionation step, and nano-scale liquid chromatographic tandem mass spectrometry (nLC-MS/MS) analysis. The results highlighted an evident improvement of proteome extraction by the combination of phenol extraction with SDS-PAGE before the nLC-MS/MS analysis. In addition, a dramatic impact of the steaming process (the treatment to produce red ginseng from ginseng) on protein properties was observed. Overall, the analyses of Korean ginseng permitted the characterization of a total of 2412 proteins. A large number of identified proteins belonged to the functional categories of protein and carbon/energy metabolism (22.4% and 14.6%, respectively). The primary and secondary metabolisms are major metabolic pathways, which emerged from the proteomic analysis. In addition, a large number of proteins known to play an important role in response to (a)biotic stresses were also identified. The current proteomic study not only confirmed the previous transcriptomic and proteomic reports but also extended proteomic information, including the main metabolic pathways involved in Korean ginseng. Full article

This study explored the effects of peanut shell biochar (PSB) on the adsorption capacities of fungicides with and without successive chemical modifications, using KMnO₄ and KOH (PSB_OX-A), in order to provide a valuable understanding of their adsorption mechanisms and behaviors. To this end, the physicochemical properties of PSB and PSB_OX-A were examined by using the Brunauer–Emmett–Teller method, Fourier transform infrared spectroscopy, and scanning electron microscopy with an energy dispersive X-ray spectrometer. The effects of temperature, ionic strength, and humic acids on the adsorption of fungicides, using PSB and PSB_OX-A, were estimated through batch experiments. Furthermore, adsorption kinetics, isotherms, and thermodynamics were studied. The maximum adsorption capacities of fungicides by PSB_OX-A were estimated to be more notable (Q_max of carbendazim = 531.2 μmol g⁻¹, Q_max of pyrimethanil = 467.7 μmol g⁻¹, and Q_max of tebuconazole = 495.1 μmol g⁻¹) than PSB (Q_max of carbendazim = 92.6 μmol g⁻¹, Q_max of pyrimethanil = 61.7 μmol g⁻¹, and Q_max of tebuconazole = 66.7 μmol g⁻¹). These findings suggest that successive chemical modification using KMnO₄ and KOH could potentially be used to effectively fabricate PSB to remove fungicides in water-treatment processes. Full article

The fatty acid compositions, including isomer compositions, of seven seed oils containing conjugated fatty acids (CFA) were determined. Seed oils were extracted using a modified Folch extraction, converted to fatty acid methyl esters, and analyzed by gas chromatography (GC) with mass spectrometry and flame ionization detection. The MS detector was operated in positive-ion chemical ionization mode using methane reagent gas. GC was performed using two columns providing different retention characteristics: a poly(ethylene glycol) column and a more polar biscyanopropyl column. The complimentary information provided by the two columns was crucial to peak identification in several cases. The major CFA species in the samples are well known but all contained lesser amounts of additional CFA that have not been widely reported. All samples contained multiple species of conjugated linolenic acid, and two samples also contained small amounts of conjugated linoleic acid. The seed oils of Jacaranda mimosifolia and Calendula officinalis were found to contain 8c,10t,12t-18:3, the natural occurrence of which has only been recently reported in some other samples. The seed oil of Impatiens balsamina has been reported to contain four conjugated 18:4 species, and we present evidence for a fifth conjugated 18:4 isomer. Full article

New composite adsorbents including silica supports (silica, aerosilogel, and diatomite) and carbon materials (multiwall carbon nanotubes and pyrolytic carbon) have been prepared and characterized. The analytical capabilities of the produced sorbents have been evaluated by their efficiency in the express pre-concentration of volatile organic compounds (butanol and phenols) from the air stream. The prepared surface-layered adsorbents containing multiwall carbon nanotubes placed onto the surface of aerosilogel by use of the carbon vapor deposition method with preloading cobalt nanostructures as a catalyst were found significantly more efficient than traditionally used graphitic carbon-based adsorbents Carbopacks B, C, and X. Additionally, a new adsorbent composed of diatomite Porochrome-3 support coated with a pyrocarbon layer was prepared. This low surface area composited adsorbent allowed both quantitative pre-concentration of phenol and isomeric cresols from the air and their thermal desorption. The developed adsorbents provided fast pre-concentration of selected phenols with a concentration factor of 2 × 10³ in 5 min and were used for gas chromatographic determination of analytes in the air at low concentration levels starting from several μg/m³ with a flame ionization detector. Full article

The dissociation constant is an important physicochemical property of drug molecules that affects the pharmacokinetic and pharmacodynamic properties of drugs. In this study, the distribution coefficients of 16 active ingredients extracted from herbal materials were determined at different pH values in liquid–liquid equilibrium systems; the active ingredients were sinomenine, aescin A, aescin B, aescin C, aescin D, chlorogenic acid, neochlorogenic acid, cryptochlorogenic acid, isochlorogenic acid A, isochlorogenic acid B, isochlorogenic acid C, baicalin, wogonoside, calycosin-7-glucoside, astraisoflavan-7-O-β-D-glucoside, and isomucronulatol 7-O-glucoside. The dissociation constants of these active ingredients were calibrated and compared with reported values. The dissociation constants obtained were close to those reported in other studies, which means that the results of this work are reliable. Full article

Thiophenic compounds constitute a class of sulfur compounds derived by thiophene, containing at least one thiophenic ring. Their presence in fuels (crude oil, etc.) is important and can reach 3% m/m. The combustion of fuels leads to the formation of sulfur oxides a severe source of environmental pollution issues, such as acid rain with adverse effects both to humans and to the environment. To reduce such problems, the EU and other regulatory agencies worldwide set increasingly stringent regulations for sulfur content in fuels resulting in the necessity for intense desulphurization processes. However, most of these processes are inefficient in the total removal of sulfur compounds. Therefore, thiophenic compounds such as benzothiophenes and dibenzothiophenes are still present in heavier fractions of petroleum, therefore, their determination is of great importance. Until now, all HPLC methods applied in similar studies use gradient elution programs that may last more than 25 min with no validation results provided. To fill this gap, the aim of the present study was to develop and validate a simple and fast HPLC-UV method in order to be used as a useful monitoring tool in the evaluation studies of novel desulfurization technologies by means of simultaneous determination of dibenzothiophene (DBT) and 4,6-dimethyl-dibenzothiophene and dibenzothiophene sulfone in the desulfurization effluents. Full article

Ferrofluids (FFs) constitute a type of tunable magnetic material, formed by magnetic nanoparticles suspended in a liquid carrier. The astonishing magnetic properties of these materials and their liquid nature have led to their extended use in different applications, including fields such as magnetochemistry, optics, and biomedicine, among others. Recently, FFs have been incorporated as extractant materials in magnetic-driven analytical sample preparation procedures, thus, permitting the development of different applications. FF-based extraction takes advantage of both the magnetic susceptibility of the nanoparticles and the properties of the liquid carrier, which are responsible for a wide variety of interactions with analytes and ultimately are a key factor in achieving better extraction performance. This review article classifies existing FFs in terms of the solvent used as a carrier (organic solvents, water, ionic liquids, deep eutectic solvents, and supramolecular solvents) while overviewing the most relevant analytical applications in the last decade. Full article

Niacin is a water-soluble vitamin whose deficiency causes many disorders and diseases, including pellagra and high blood cholesterol. Herein, niacin and four common impurities, isonicotinic acid (ISO), 5-ethyl-2-methylpyridine (MP), pyridine-2, 5-dicarboxylic acid (PDC) and pyridine PYR, are simultaneously analyzed, where PYR is known as potentially nephrotoxic and hepatotoxic. The separation of a mixture using gas chromatography–mass spectroscopy (GC–MS) without any derivatization steps was the main target. Many studies have been published to study Niacin and its impurities using colorimetry and HPLC. GC–MS was selected to study the analyzed mixture owing to its known sensitivity and selectivity. In this study, a single quadrupole mass spectrometer operated in selected ion monitoring (SIM) mode at an electron ionization energy of 70 eV was applied for the quantitative analysis of Niacin. Helium was used as the carrier gas and adjusted to run through an HP-5ms (5%-phenyl)-methylpolysiloxane column. Statistical analysis proved that this method is equally effective as the previously reported method. Importantly, this study was eco-friendly as compared to the reported high performance thin layer chromatographic method (HPTLC). Finally, this study provides a new and valid eco-friendly method analysis to determine the concentration of niacin and its common impurities at very low concentration. Conclusion: A simple, rapid accurate and green GC–MS analytical method was developed and validated to determine niacin and its related official impurities. Full article

Phenolic composition of green tea (Camellia sinensis) varies according to manufacturing processes that result in deglycosylation of glycosylated phenolics and condensation, epimerization, and degalloylation of flavan-3-ols (catechins). Ambiguous phenolic assignments based on UV absorbance alone can occur when the chromatographic peaks overlapped slightly. We established an improved method using an HPLC–UV coupled with a single-quadrupole MS detector (MS¹) that can reject false UV peaks after checking the preceding MS¹ peaks. Adjusted UV data coded by the Python algorithm were deployed to compare tea phenolics. Performance validation of the MS¹ and UV analysis methods for 19 phenolics revealed a sensitivity of 0.17 and 0.47 pmol/injection, limit of detection of 15 and 33 μg/L, limit of quantification of 50 and 110 μg/L, intra-day precision of 5% and 1% relative standard deviation, and trueness of 83–135% and 97–100%, respectively. Our results suggest that the HPLC–UV–MS¹ method, which is a low operational cost method, potentially provides the precise phenolic composition of teas. Full article

Periploca aphylla (PA), an interesting Saudi medicinal plant, is used in folk medicine to treat urticaria, cerebral fever, tumors, and swelling. To prove its use in folk medicine, two different extracts from the aerial parts of the plant: chloroform P-1, and n-butanol P-2 were subjected to biological assays to screen peroxisome proliferator-activated receptors (PPARα and PPARγ) agnostic, anti-inflammatory, antioxidant, cytotoxic, and estrogenic activities. In addition, five bioactive secondary metabolites were isolated from the aerial parts of the plant: rutin, chlorogenic acid, caffeic acid, ursolic acid, and stigmasterol. P-1 and P-2 decreased cellular oxidative stress by 47.0% and 62.0%, respectively, compared to the standard drug quercetin, while one of the compounds rutin PA-1 isolated from P-1 extract and significantly decreased cellular oxidative stress by 67.0% compared to quercetin (75.0%). P-1 and P-2 also significantly activated PPARγ agnostic. P-1 and P-2 did not inhibit nuclear factor kappa B and inducible nitric oxide synthase activity and showed no cytotoxic or estergenic effects on four human cancer cell lines. In this study, both extracts were standardized using high-performance thin-layer chromatography (HPTLC). RP-HPTLC showed sharp and compact bands of rutin (R_f = 0.09), caffeic acid (R_f = 0.25), and chlorogenic acid (R_f = 0.39) scanned at λ_max = 340 nm using the water: methanol (60:40 v/v) mobile phase. At λ_max = 539 nm ursolic acid (R_f = 0.20) and stigmasterol (R_f = 0.48) were scanned using the chloroform: methanol (98:2 v/v) as NP-HPTLC mobile phase. Therefore, the developed RP- and NP-HPTLC systems are a precise, sensitive, and specific analytical tool for the quantification of compounds isolated from PA, which can be used as phytomarkers for taxonomical identification and assessment of PA. Full article

In this study, a low-cost, efficient, and environmentally friendly anaerobic sludge process for the treatment of industrial beverage wastewater was investigated to analyze the effect of bacteria growth on the degradation of organic matter (chemical oxygen demand). Additionally, the mechanism, interactions between the microbe’s growth, and operating conditions of an anaerobic batch reactor along with the wastewater treatment efficiency were evaluated via microbial kinetics. The kinetic coefficients based on chemical oxygen demand (COD) by conventional techniques such as kinetic coefficients growth yield (0.46 mg VSS/mg COD), saturation coefficient (3500 mg/L COD), the maximum rate of substrate utilization per unit mass of biomass (0.0066 mg/L COD), growth rate by Monod equation, M (0.03833 L/h), and maximum growth rate, μm (0.03672 L/h) were calculated. The results show a higher rate of substrate degradation (0.54 day⁻¹) due to the high COD removal efficiency (CRE) of 99.31% during 13 days that was achieved, which can be attributed to the active involvement of anaerobic microbes in the process of degradation. Based on these results, it can be concluded that the current study can be used as an effective way to analyze the industrial beverage wastewater at commercial levels. Full article

Dyes are a type of pollutant that have been discharged into water streams by various industries and had harmful effects on the environment and human health. Therefore, present work was directed to recycle acrylic fibers waste to be used as an adsorbent to exclude dyes such as methylene blue (MB) and Congo red (CR) from dyes-polluted wastewater. Acrylic fibers waste was converted into membrane followed by chemical grafting with p-phenylenediamine monomer to form functional modified membranes. Afterwards, some characterization analyses; Fourier transform-infrared, scanning electron microscope, swelling behavior, and porosity properties were performed for the acrylic fiber grafted membrane (AFGM). For obtaining the best conditions that permit the highest adsorption capacity of the AFGM, some preliminary experiments followed by general full factorial design experiments were displayed. Langmuir, Freundlich isotherms and kinetic studies evaluations were applied. Results revealed that, the adsorption capacities of the AFGM were 61% for Methylene blue and 86% for Congo red that stated the high affinity of the AFGM to the anionic dyes. The reusability of the AFGM membranes in different cycles for 3Rs processes “Removal, Recovery, and Re-use” indicated the efficiency of the AFGM to be used in wastewater treatment. Full article

The article revisits the discrete recurrence method to model the instruments of liquid–liquid partition chromatography as counter-current chromatography (CCC) and centrifugal partition chromatography (CPC). The purpose is to simplify the computation of the concentration profiles without supplementary approximations, rather by going back to the seminal model of binomial random walks, associated with the stochastic master equation that generates simple discrete recurrence relations. It fits the model of the prototype of liquid–liquid chromatography: the Craig’s apparatus. Three emblematic separation technique group cases are computed in batch injection, batch multiple dual mode (MDM), and continuous injection by the “True Moving Bed” (TMB) in CPC. Full article

The selective separation and recovery of specific platinum-group metals (PGMs) from metal mixtures is a significant challenge owing to the similarity of these metals in terms of chemical and physical properties. Among the typical PGMs (Pd, Pt, and Rh), the selective recovery of Pt prior to the recovery of Pd and Rh is in high demand. In this study, we attempted the selective precipitation of Pt(IV) from mixed-metal HCl solutions using 2-ethylhexylamine (2EHA) as a precipitant and achieved the selective precipitation of Pt(IV) from Pd(II) and Rh(III) over a wide range of HCl concentrations. Selective precipitation of Pt(IV) was also achieved from HCl solutions with high levels of base metals, such as Al, Cu, Fe, and Zn. High yields of undegraded 2EHA remaining in the HCl solution after Pt(IV) precipitation were recovered using hydrophobic porous resins. X-ray photoelectron spectroscopy and thermogravimetric measurements revealed that the Pt(IV)-containing precipitate was an ion-pair comprising one [PtCl₆]²⁻ and two ammonium cations of 2EHA. The steric hindrance and high hydrophilicity of 2EHA suppressed the formation of Rh(III)- and Pd(II)-containing precipitates, respectively, resulting in the selective precipitation of Pt(IV). Full article

The pollution of freshwater resources with crude petroleum oil is a major environmental issue in oil-producing countries. As a result, the remediation of polluted aquatic ecosystems using eco-friendly and cost-effective technology is receiving increased global attention. In this study, the ability of Azolla pinnata R. Br. to remediate petroleum-polluted freshwater was assessed. The remediation potentiality was determined by evaluating the total petroleum hydrocarbon degradation percentage (TPH%) and changes in the molecular type composition of saturated and aromatic hydrocarbon fractions. TPH% was estimated gravimetrically, and changes in the molecular type composition of saturated and aromatic fractions were measured using gas chromatography and high-performance liquid chromatography, respectively. The results reveal that A. pinnata has the potential to phytoremediate freshwater polluted with low levels (up to 0.5 g/L) of petroleum hydrocarbons (PHs). After seven days of phytoremediation, the degradation rate of total PHs was 92% in the planted treatment compared with 38% in the unplanted positive control. The highest breakdown of PHs for the normal paraffinic saturated hydrocarbon fraction occurred in the presence of A. pinnata combined with Anabena azollaea (A-A), which showed a moderate degradation capacity toward total aromatic hydrocarbons (TAHs) and total polycyclic aromatic hydrocarbons (PAHs). The results indicate that A. pinnata effectively removed C18, a saturated PH, and acenaphthene (Ace), an aromatic PH. Therefore, this study suggests that A. pinnata is a useful tool for the remediation of freshwaters contaminated with low pollution levels of crude oil. Full article

Knowledge of the type and level of saturated and unsaturated fatty acids in food and clinical matrices is of practical importance, but the wide variety of fatty acids makes analyses very complex. The discrimination of the geometric isomers of fatty acid needs proper and effective separation conditions. The efficiency of three different stationary phases was evaluated by GC–MS methods in the separation of fatty acids in their methyl ester forms. Significant differences were observed in the efficiencies of polysiloxane-based (non-polar HP-5MS and medium/high polarity DB-225MS) and ionic liquid-based (SLB-IL111) columns. Baseline separation of the geometric isomers of linoleic acid methyl ester was obtained by the extremely polar SLB-IL111 column, showing a preference over the other two columns. The optimization of the experimental conditions (response linearity, limit of detection, limit of quantification, system suitability, intraday and interday repeatability and accuracy) showed the separation power of the ionic liquid interaction in the analyses by using short (25–30 m long) columns. By deducting the general principles of the interaction, predictions can be made for the separation of other isomers. The results facilitate the precise identification of various types of fatty acids in real samples for nutritional information. Full article

Perchlorate ion (ClO₄⁻) is known as a potent endocrine disruptor and exposure to this compound can result in serious health issues. It has been found in drinking water, swimming pools, and surface water in many countries, however, its occurrence in the environment is still poorly understood. The information on perchlorate contamination of Polish waters is very limited. The primary objective of this study was to assess ClO₄⁻ content in bottled, tap, river, and swimming pool water samples from different regions of Poland and provide some data on the presence of perchlorate. We have examined samples of bottled, river, municipal, and swimming pool water using the IC–CD (ion chromatography–conductivity detection) method. Limit of detection and limit of quantification were 0.43 µg/L and 1.42 µg/L, respectively, and they were both above the current health advisory levels in drinking water. The concentration of perchlorate were found to be 3.12 µg/L in one river water sample and from 6.38 to 8.14 µg/L in swimming pool water samples. Importantly, the level of perchlorate was below the limit of detection (LOD) in all bottled water samples. The results have shown that the determined perchlorate contamination in Polish drinking waters seems to be small, nevertheless, further studies are required on surface and river samples. The inexpensive, fast, and sensitive IC–CD method used in this study allowed for a reliable determination of perchlorate in the analyzed samples. To the best of our knowledge, there are no other studies seeking to assess the perchlorate content in Polish waters. Full article

The movement of the gas–liquid interface caused by the movement of the bubble position will have an impact on the starting conditions for particle migration. This article quantifies the influence of moving bubbles on the starting conditions of particle migration in non-Newtonian fluids, and it aims to better understand the influence of bubbles moving in non-Newtonian fluids on particle migration to achieve more effective control. First, the forces and moments acting on the particles are analyzed; then, fluid dynamics, non-Newtonian fluid mechanics, extended DLVO (Derjaguin Landau Verwey Overbeek theory), surface tension, and friction are applied on the combined effects of particle migration. Then, we reasonably predict the influence of gas–liquid interface movement on particle migration in non-Newtonian fluids. The theoretical results show that the movement of the gas–liquid interface in non-Newtonian fluids will increase the separation force acting on the particles, which will lead to particle migration. Second, we carry out the particle migration experiment of moving bubbles in non-Newtonian fluid. Experiments show that when the solid–liquid two-phase flow is originally stable, particle migration occurs after the bubble movement is added. This phenomenon shows that the non-Newtonian fluid with bubble motion has stronger particle migration ability. Although there are some errors, the experimental results basically support the theoretical data. Full article