Solid-phase Extraction Protocol Research Articles

Distribution, chemical, and molecular composition of high and low molecular weight humic-like substances in ambient aerosols

Abstract. Humic-like substances (HULIS) encompass a continuum of molecular weight (MW) ranges, yet our understanding of how HULIS characteristics vary with MW is still limited and not well established. In this study, a combination of ultrafiltration and solid-phase extraction protocols was employed to fractionate the high MW (HMW; > 1 kDa) and low MW (LMW; < 1 kDa) HULIS fractions from ambient aerosols collected during summer and winter at a rural site. Subsequently, comprehensive characterization using total organic carbon, high-performance size exclusion chromatography (HPSEC), UV-visible (UV-vis) and fluorescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), and negative electrospray ionization high-resolution mass spectrometry (ESI–HRMS) were conducted. The results revealed that HMW HULIS were dominated by larger-sized chromophores, substantially constituting a higher fraction of total organic carbon and UV absorption at 254 nm than LMW HULIS. While both HMW and LMW HULIS shared similar fluorophore types and functional groups, the former exhibited higher levels of humification and a greater presence of polar functional groups (e.g., −COOH; > C=O). HRMS analysis further unveiled that molecular formulas within HMW HULIS generally featured smaller sizes but higher degrees of unsaturation and aromaticity compared to those within LMW HULIS fractions. This observation suggests the possibility of small molecules assembling to form the HMW HULIS through intermolecular weak forces. Moreover, HMW HULIS contained a higher proportion of CHON but fewer CHO compounds than LMW HULIS. In both HMW and LMW HULIS, the unique molecular formulas were primarily characterized by lignin-like species, yet the former displayed a prevalence of N-enriched and highly aromatic species. Additionally, HMW HULIS contained more unique lipid-like compounds, while LMW HULIS exhibited a distinct presence of tannin-like compounds. These findings provide valuable insights into the distribution, optical properties, and molecular-level characteristics of HULIS in atmospheric aerosols, thereby advancing our understanding of their sources, composition, and environmental implications.

Determination of atropine and scopolamine in honey using a miniaturized polymer-based solid-phase extraction protocol prior to the analysis by HPLC-MS/MS

Two homopolymers have been prepared employing methacrylic acid and 4-vynylpiridine as functional monomers (p-MAA, p-4-VP) through an easy and quick precipitation polymerization method for application as sorbents in solid-phase extraction (SPE) to determine atropine and scopolamine in honey. The optimized SPE conditions were as follows: 25 mg of p-MAA, 4 mL of sample loading volume (diluted honey 1:10 with water), 4 mL of elution solvent (methanol/water with 1 % formic acid, 80/20, v/v). The extracts were analyzed by HPLC-MS/MS. The cartridges were reusable for forty cycles demonstrating an environmentally friendly approach. The methodology was validated in terms of linearity, accuracy, precision, selectivity, matrix effect and sensibility, highlighting the absence of matrix effect. The miniaturized polymer-based SPE was successfully applied to fifteen honeys, showing concentrations up to 7.23 ng/g in the most contaminated honey. All quantified honey samples (5 in total) were of multifloral type.

Development of a molecularly imprinted membrane for selective, high-sensitive, and on-site detection of antibiotics in waters and drugs: Application for sulfamethoxazole

Sulfonamides are among the widespread bacterial antibiotics. Despite this, their quick emergence constitutes a serious problem for ecosystems and human health. Therefore, there is an increased interest in developing relevant detection method for antibiotics in different matrices. In this work, a straightforward, green, and cost-effective protocol was proposed for the preparation of a selective molecularly imprinted membrane (MIM) of sulfamethoxazole (SMX), a commonly used antibiotic. Thus, cellulose acetate was used as the functional polymer, while polyethylene glycol served as a pore-former. The developed MIM was successfully characterized through scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The MIM was used as a sensing platform in conjunction with a smartphone for optical readout, enabling on-site, selective, and highly sensitive detection of SMX. In this way, a satisfactory imprinting factor of around 3.6 and a limit of detection of 2 ng mL−1 were reached after applying response surface methodologies, including Box-Behnken and central composite designs. Besides, MIM demonstrated its applicability for the accurate and selective detection of SMX in river waters, wastewater, and drugs. Additionally, the MIM was shown to be a valuable sorbent in a solid-phase extraction protocol, employing a spin column setup that offered rapid and reproducible results. Furthermore, the developed sensing platform exhibited notable regeneration properties over multiple cycles and long shelf-life in different storage conditions. The newly developed methodology is of crucial importance to overcome the limitations of classical imprinting polymers. Furthermore, the smartphone-based platform was used to surpass the typically expensive and complicated methods of detection.

Imipramine-imprinted polymer: Designing by theoretical and empirical studies

In this study the model drug imipramine was used to elaborate a theoretical protocol for the evaluation of the selectivity of molecularly imprinted polymer (MIP) system towards the drug and its main metabolite, viz. imipramine and desipramine for the bioanalytical purpose. The MIP1 prepared from 4-vinylbenzoic acid disclosed the highest binding capacity (8.3 ± 1.6 µg g−1) and the lowest ΔEB (–200.88 kcal mol−1) among all tested MIP systems together with the highest specificity with imprinting factor close to 16. The morphological and thermoanalytical measurements confirmed differences between MIP1 and NIP1 with the total specific surface areas equal to 147.2 m2 g−1 and 129.4 m2 g−1, respectively. The selectivity study revealed the highest binding capacities for imipramine and its close structural analogs, viz. maprotyline and protriptyline. The optimized experimental molecularly imprinted solid phase extraction protocol for MIP1 allowed for the recovery of imipramine and its main metabolite, desipramine from spiked human plasma samples with 108% and 69%, respectively, verifying positively the elaborated theoretical model.

Application of a homemade silica-based mixed-mode ion-exchange sorbent for the determination of drugs in environmental water samples

Two homemade silica-based mixed-mode ion-exchange sorbents with strong moieties were compared for the solid-phase extraction (SPE) of a group of pharmaceuticals, drugs of abuse and metabolites. The difference between sorbents was the presence of graphene microparticles embedded in the network and the best results were obtained with the sorbent that did not contain graphene. The optimum SPE protocol of the non-graphene sorbent was: loading pH at 3, different loading volumes depending on the type of sample, 2 mL of MeOH as washing solvent. The optimized method was validated for the analysis of water samples of environmental interest (river water, effluent wastewater and influent wastewater). Apparent recoveries ranged from 22 to 68%, matrix effect values were lower than ±20 for most compounds, and method detection limits ranged from 1 to 28 ng/L and method quantification limits from 2 to 56 ng/L. Precision was obtained as percentual relative standard deviation (RSD%, n=4) and the repeatability and reproducibility between days were always lower than 18%. The sorbent was used to determine the analytes in environmental water samples, where most compounds were found in the range from 2 to 180 ng/L in river samples, from 3 to 2547 ng/L in effluent wastewater samples and from 24 to 8086 ng/L in influent wastewater samples.

Application of urea-based magnetic covalent organic framework as sorbent for the determination of coumarin and its derivatives in food samples combined with liquid chromatography-mass spectrometry

A magnetic solid-phase extraction (MSPE) protocol using novel Urea-based magnetic covalent organic framework coupled with liquid chromatography-mass spectrometry was developed for the detection of coumarins in food samples (soft drink, biscuit and sesame paste). This adsorbent was synthesized through atom economic polymerization of tetrakis(4-aminophenyl) methane and 1,4-phenylene diisocyanate, which was successfully verified by a series of techniques. Major parameters influencing MSPE efficiency were optimized. This protocol had some advantages, such as organic-reagent-saving (2.0 mL), easy operating, short extraction time, and high repeatability (8 times). The established method exhibited superior linearity (R2 ≥ 0.999) and the limits of detection ranging from 1.0 to 5.0 µg/kg. The recoveries of coumarin and its derivatives ranged from 73.8% to 113.5% and both intra- and inter-day precision were less than 15%. These data indicate the protocol is a highly promising alternative for coumarin extraction and enrichment.

Aptamer-modified magnetic nanoparticles for extraction of atrazine in environmental water samples

In this work, a novel aptamer magnetic sorbent was prepared and used as magnetic solid-phase extraction sorbent for selective isolation of atrazine (ATZ) in water samples. The magnetic oligosorbent was fabricated by immobilizing DNA aptamer onto the surface of vinylized magnetic nanoparticles (VMNPs) via “thiol-ene” click chemistry reaction. After optimization of different aptamer coupling parameters, the following experimental conditions were found to give best results: 100 mg VMNPs incubated with 1 μmol L−1 thiol-modified aptamer for 5 h at 55 °C. The resulting oligosorbent was characterized by different instrumental techniques such as transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and inductively coupled plasma mass spectrometry (ICP-MS). Then, several parameters of the extraction protocol were investigated to achieve the best ATZ extraction performance. The optimized aptamer-based magnetic solid-phase extraction (Apt-MSPE) protocol followed by HPLC with diode-array detection gave detection and quantification limits for ATZ of 0.005 µg L−1 and 0.018 µg L−1, respectively. The applicability of this protocol was demonstrated by analyzing several environmental water samples from of different sources with recovery values from 85.5 to 94% and relative standard deviations less than 2.5%. Moreover, the developed Apt-MNPs sorbent could be re-used at least 12 times, without losses in its extraction capacity.

Qualitative Analysis of Polyphenols in Glycerol Plant Extracts Using Untargeted Metabolomics.

Glycerol is a reliable solvent for extracting polyphenols from food and waste products. There has been an increase in the application of glycerol over benchmark alcoholic solvents such as ethanol and methanol for natural product generation because of its non-toxic nature and high extraction efficiency. However, plant extracts containing a high glycerol concentration are unsuitable for mass spectrometry-based investigation utilising electrospray ionization, inhibiting the ability to analyse compounds of interest. In this investigation, a solid phase extraction protocol is outlined for removing glycerol from plant extracts containing a high concentration of glycerol and their subsequent analysis of polyphenols using ultra-performance liquid chromatography coupled with quadrupole time of flight tandem mass spectrometry. Using this method, glycerol-based extracts of Queen Garnet Plum (Prunus salicina) were investigated and compared to ethanolic extracts. Anthocyanins and flavonoids in high abundance were found in both glycerol and ethanol extracts. The polyphenol metabolome of Queen Garnet Plum was 53% polyphenol glycoside derivatives and 47% polyphenols in their aglycone forms. Furthermore, 56% of the flavonoid derivates were found to be flavonoid glycosides, and 44% were flavonoid aglycones. In addition, two flavonoid glycosides not previously found in Queen Garnet Plum were putatively identified: Quercetin-3-O-xyloside and Quercetin-3-O-rhamnoside.

Study on the Occurrence of Artificial Sweeteners, Parabens, and Other Emerging Contaminants in Hospital Wastewater Using LC-QToF-MS Target Screening Approach

The presence of 220 emerging contaminants belonging to different classes (artificial sweeteners, personal care products, coffee and tobacco-related compounds, and industrial chemicals) was investigated in hospital wastewater for the first time. Twenty samples were collected within two sampling periods from two points of a Greek General Hospital. Target compounds were analyzed using a solid-phase extraction protocol followed by UHPLC-ESI-QToF-MS analysis. Analytical results showed that 23 micropollutants were detected at least once in hospital wastewater samples in Period 1, while 27 compounds were detected at least once in Period 2. The coffee and tobacco-related compounds were the most frequently detected substances, followed by artificial sweeteners, parabens, and industrial chemicals. The highest mean concentrations were recorded for the artificial sweeteners cyclamic acid (377 μg/L) and saccharine (295 μg/L), followed by caffeine (193 μg/L), nicotine (162 μg/L), and the industrial chemical lauryl diethanolamide (153 μg/L). The group of artificial sweeteners contributed up to 55.1% (Point A/Period 1) to the total concentration of studied chemicals. The detection of high concentrations of artificial sweeteners in hospital effluents reveals that hospitals should be considered as important point-sources of these contaminants.

Investigation of Imidazolium-Based Ionic Liquids as Additives for the Separation of Urinary Biogenic Amines via Capillary Electrophoresis

Ionic liquids (ILs), such as imidazoles, can be used to prevent the sorption of analytes onto the walls of the capillary. Prior works have confirmed that coating the capillary wall with a cationic layer can increase its surface stability, thereby improving the repeatability of the separation process. In this study, micellar electrokinetic chromatography (MEKC) is employed to evaluate how two ILs with different anions—namely, 1-hexyl-3-methylimidazolium chloride [HMIM+Cl−] and 1-hexyl-3-methylimidazolium tetrafluoroborate [HMIM+BF4−]—affect the separation efficiency for biogenic amines (BAs) such as metanephrine (M), normetanephrine (NM), vanilmandelic acid (VMA), and homovanillic acid (HVA) in urine samples. To this end, solid-phase extraction (SPE) is employed using different sample pH values, with the results demonstrating that HVA and VMA is easily extracted at a sample pH of 5.5, while a sample pH of 9.0 facilitated the extraction of M and NM. In the applied SPE protocol, selected analytes were isolated from urine samples using hydrophilic–lipophilic-balanced (HLB) columns and eluted with methanol (MeOH). The validation data confirmed the method’s linearity (R2 > 0.996) for all analytes within the range of 0.25–10 µg/mL. The applicability of the optimized SPE-MEKC-UV method was confirmed by employing it to quantify clinically relevant BAs in real urine samples from pediatric neuroblastoma (NBL) patients.

Extraction of selected benzothiazoles, benzotriazoles and benzenesulfonamides from environmental water samples using a home-made sol-gel silica-based mixed-mode zwitterionic sorbent modified with graphene

A novel sol-gel silica-based mixed-mode zwitterionic sorbent modified with graphene microparticles was synthesized. Thanks to the inclusion of multiple functional groups and graphene microparticles to exert a wide range of intermolecular/interionic interactions including dipole-dipole interactions, ion-exchange interactions and π-π interactions, the sorbent showed high retention in the solid-phase extraction (SPE) of benzothiazoles, benzotriazoles and benzenesulfonamides.The SPE protocol was optimized in terms of pH, sample loading volume and elution conditions using liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS). The method based on SPE followed by LC-HRMS was validated. Apparent recoveries at two levels of concentration were in the range from 48 to 85% (in most cases) in matrices such as influent wastewater, matrix effect was lower than ±30% in most cases, method detection and quantification limits being lower than 20 ng/L and repeatability and reproducibility between days were lower than 18% (n = 4).River, effluent and influent wastewaters samples were analyzed, obtaining concentrations ranging from 3 to 175 ng/L in river samples, from 12 to 499 ng/L in effluent samples and from 15 to 632 ng/L in influent samples, when the compounds were above the method quantification limits.

Development of ion-imprinted polymers for the selective extraction of Cu(II) ions in environmental waters

Several ion-imprinted polymers (IIPs) were synthesized via bulk polymerization with Cu(II) as template ion, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as crosslinking agent, and azobisisobutyronitrile as initiator in acetonitrile or methanol as porogen solvent. Non-imprinted polymers (NIPs) were similarly synthesized but without Cu(II). After grounding and sieving, the template ions were removed from IIPs particles through several cycles of elimination in 3 M HCl. All NIPs were equally subjected to this acid treatment with the exception of one NIP, called unwashed NIP. The resulting IIP/NIP particles were packed in solid phase extraction (SPE) cartridges for characterization. The SPE protocol was designed by optimizing a washing step following the sample percolation to eliminate potential interfering ions prior to the elution of Cu(II), all fractions analyzed by inductively coupled plasma mass spectrometry. The best IIP showed a high specificity (recovery of Cu(II) vs. interfering ions) and a good selectivity (retention on IIP vs. NIP). Its adsorption capacity was determined to be 63 μg g−1. Then, a volume of 50 mL was percolated with 30 mg of IIP, thus giving rise to an enrichment factor of 24. Finally, applications to real samples (mineral and sea waters) were successfully performed. In addition, Brunauer-Emmett-Teller analyses showed that the surface area of the washed NIP was almost double that of the unwashed one (140.70 vs. 74.49 m2 g−1), demonstrating for the first time that the post-treatment of a NIP after its synthesis may have a significant impact on its porous structure, and thus need to be more precisely detailed by authors in the future papers.

Application of a Small Protein-Coated Column to Trap, Extract and Enrich Carbamazepine Directly from Human Serum for Direct Chromatographic Analysis

An automated solid phase extraction (SPE) protocol to determine carbamazepine in human serum has been developed and validated using a simple, rabid and sensitive liquid chromatography-based bio-analytical method. Extraction of carbamazepine was carried out using an on-line SPE tool of a short protein-coated (PC) ODS silica pre-column (PC-ODS-pre-column) and phosphate buffer saline (PBS) with a pH of 7.4 as an extraction solvent. There are two distinct chromatographic modes used by PC-ODS-pre-column. While carbamazepine trapping required reversed-phase liquid chromatography, proteins were extracted from serum samples using PBS by size-exclusion liquid chromatography. Then, carbamazepine was eluted from the PC-ODS-pre-column onto the quantification position using a mixture of methanol-distilled deionized water (50:50, v/v) as an eluent and ODS analytical column. At room temperature (22 ± 1 °C), carbamazepine was completely separated from the co-eluted matrix components and detected at 230 nm. Carbamazepine’s linearity was obtained at concentrations ranging from 50 to 10,000 ng/mL. With good accuracy and precision, carbamazepine recoveries in serum samples ranged from 86.14 to 97.82%. The extraction step was conducted using PBS as a safe and green extraction solvent, making this protocol both cost-effective and ecologically safe.

Determination of steroid hormones in grey seal (Halichoerus grypus) blood plasma using convergence chromatography tandem mass spectrometry

A hybrid solid phase extraction (HybridSPE) protocol tailored to ultra-performance convergence chromatography tandem mass spectrometry (UPC2-MS/MS) was developed for the determination of 19 steroid hormones in grey seal (Halichoerus grypus) blood plasma. In this study, the protocol demonstrated acceptable absolute recoveries ranging from 33 to 90%. The chromatographic separation was carried out using a gradient elution program with a total run time of 5 min. For most target analytes, the method repeatability ranged from 1.9 to 24% and the method limits of quantification (mLOQs) ranged from 0.03 to 1.67 ng/mL. A total of 9 plasma samples were analysed to demonstrate the applicability of the developed method, and 13 steroid hormones were quantified in grey seal pup plasma. The most prevalent steroids: cortisol, cortisone, corticosterone, 11-deoxycortisol, progesterone and 17α-hydroxyprogesterone were detected at concentrations in the range of 12.6–40.1, 7.10–24.2, 0.74–10.7, 1.06–5.72, 0.38–4.38 and <mLOQ - 1.01 ng/mL, respectively. To our knowledge, this is the first study to determine steroid hormones in the plasma of pinnipeds using convergence chromatography.

Multiclass target analysis of contaminants of emerging concern including transformation products, soil bioavailability assessment and retrospective screening as tools to evaluate risks associated with reclaimed water reuse

The occurrence of 200 multiclass contaminants of emerging concern (CECs) encompassing 168 medicinal products and transformation products (TPs), 5 artificial sweeteners, 12 industrial chemicals, and 15 other compounds was investigated in influent and effluent wastewater samples collected during 7 consecutive days from 5 wastewater treatment plants (WWTPs) located in Cyprus. The methodology included a generic solid-phase extraction protocol using mixed-bed cartridges followed by Ultra-High Performance Liquid Chromatography coupled with Quadrupole-Time of Flight Mass Spectrometry (UHPLC-QTOF-MS) analysis. A total of 63 CECs were detected at least in one sample, with 52 and 55 out of the 200 compounds detected in influents and effluents, respectively. Ten (10) out of the 24 families of parent compounds and associated TPs were found in the wastewater samples (influent or effluent).1-H-benzotriazole, carbamazepine, citalopram, lamotrigine, sucralose, tramadol, and venlafaxine (>80 % frequency of appearance in effluents) were assessed with respect to their bioavailability in soil as part of different scenarios of irrigation with reclaimed water following a qualitative approach. A high score of 12 (high probability) was predicted for 2 scenarios, a low score of 3 (rare occasions) for 2 scenarios, while the rest 28 scenarios had scores 5–8 (unlikely or limited possibility) and 9–11 (possibly).Retrospective screening was performed with the use of a target database of 2466 compounds and led to the detection of 158 additional compounds (medicinal products (65), medicinal products TPs (15), illicit drugs (7), illicit drugs TPs (3), industrial chemicals (11), plant protection products (25), plant protection products TPs (10), and various other compounds (22).This work aspires to showcase how the presence of CECs in wastewater could be investigated and assessed at WWTP level, including an expert-based methodology for assessing the soil bioavailability of CECs, with the aim to develop sustainable practices and enhance reclaimed water reuse.

Development and Validation of a Sensitive and Specific LC-MS/MS Method for IWR-1-Endo, a Wnt Signaling Inhibitor: Application to a Cerebral Microdialysis Study.

IWR-1-endo, a small molecule that potently inhibits the Wnt/β-catenin signaling pathway by stabilizing the AXIN2 destruction complex, can inhibit drug efflux at the blood–brain barrier. To conduct murine cerebral microdialysis research, validated, sensitive, and reliable liquid chromatography–tandem mass spectrometry (LC-MS/MS) methods were used to determine IWR-1-endo concentration in the murine plasma and brain microdialysate. IWR-1-endo and the internal standard (ISTD) dabrafenib were extracted from murine plasma and microdialysate samples by a simple solid-phase extraction protocol performed on an Oasis HLB µElution plate. Chromatographic separation was executed on a Kinetex C18 (100A, 50 × 2.1 mm, 4 µm particle size) column with a binary gradient of water and acetonitrile, each having 0.1% formic acid, pumped at a flow rate of 0.6 mL/min. Detection by mass spectrometry was conducted in the positive selected reaction monitoring ion mode by monitoring mass transitions 410.40 > 344.10 (IWR-1-endo) and 520.40 > 307.20 (ISTD). The validated curve range of IWR-1-endo was 5–1000 ng/mL for the murine plasma method (r2 ≥ 0.99) and 0.5–500 ng/mL for the microdialysate method (r2 ≥ 0.99). The lower limit of quantification (LLOQ) was 5 ng/mL and 0.5 ng/mL for the murine plasma and microdialysate sample analysis method, respectively. Negligible matrix effects were observed in murine plasma and microdialysate samples. IWR-1-endo was extremely unstable in murine plasma. To improve the stability of IWR-1-endo, pH adjustments of 1.5 were introduced to murine plasma and microdialysate samples before sample storage and processing. With pH adjustment of 1.5 to the murine plasma and microdialysate samples, IWR-1-endo was stable across several tested conditions such as benchtop, autosampler, freeze–thaw, and long term at −80 °C. The LC-MS/MS methods were successfully applied to a murine pharmacokinetic and cerebral microdialysis study to characterize the unbound IWR-1-endo exposure in brain extracellular fluid and plasma.

The Determination of Polycyclic Aromatic Hydrocarbons (PAHs) with HPLC-DAD-FLD and GC-MS Techniques in the Dissolved and Particulate Phase of Road-Tunnel Wash Water: A Case Study for Cross-Array Comparisons and Applications.

Accelerated solvent extraction (ASE) and solid phase extraction (SPE) protocols tailored to either gas chromatography mass spectrometry (GC-MS) or high-performance liquid chromatography coupled to diode-array and fluorescence detection (HPLC-DAD-FLD) were developed for the determination of EPA 16 polycyclic aromatic hydrocarbons (PAHs) in the particulate and dissolved phase of road-tunnel wash water. An analytical approach was developed, assessed, and applied on environmental samples collected from five road tunnels in Norway. The absolute recoveries ranged from 57 to 104% for the particulates, and from 42 to 79% for the dissolved water phase. The target PAH compounds were separated in 34.75 min using the GC method and in 22.50 min by HPLC. In the particulate phases, higher molecular weight PAHs were detected in the range of 0.043 to 0.93 µg/g, and lower molecular weight PAHs were detected in the range of 0.020 to 1.0 µg/g, while the intermediate ones were present in the range of 0.075 to 2.0 µg/g. In contrast to the particulates, the dissolved phase mainly contained lower molecular weight PAHs in the range of 0.0098 to 0.50 µg/L. GC-MS demonstrated lower detection limits (LODs) than HPLC-DAD-FLD for 13 out of the 16 PAHs. A cross-array comparison of the two analytical techniques indicated that some target PAHs were detected solely or in higher concentrations with HPLC-DAD-FLD, indicating the occurrence of false positive peaks or/and co-eluting components. The resulting concentrations in the road tunnel wash water samples were used to calculate specific PAH forensic ratios to pinpoint the potential sources of PAH pollution. These ratios revealed that there are several potential sources for the origin of PAHs in tunnel wash water.

Back Cover: A novel sensitive analytical method for the simultaneous analysis of vancomycin and teicoplanin in human urine via single HPLC coupled with Photodiode array and Mass Spectrometry in series

DOI: 10.1002/jssc.202200002 The cover picture shows a novel analytical protocol using single HPLC coupled with photodiode array and mass spectrometry in series, for the simultaneous determination of two glycopeptides with structural similarities: vancomycin and teicoplanin in human urine. According to the cover picture, for the treatment of the urine samples, a solid phase extraction protocol was developed and optimized, making the specific analytical method more sensitive and reliable for the simultaneous determination of these glycopeptides in difficult matrices such as urine samples.

A One-Step Polyphenol Removal Approach for Detection of Multiple Phytohormones from Grape Berry

Phytohormones play an important role in regulating the maturation process and the quality-related metabolite accumulation of fruits, and their concentration variation has always been concerned during fruit development. However, berry fruits, such as grape berries, are rich in a large number of secondary metabolites, which brings great challenges to the isolation and determination of hormones. In this work, we used grapes as experimental materials and proposed a solid-phase extraction (SPE) protocol to efficiently isolate multiple hormones from phenol-rich matrix using a mixture of dichloromethane, methanol and formic acid as eluent. A highly sensitive method based on ultra-high-performance liquid chromatography–tandem mass spectrometry (UHPLC-MS/MS) was developed to quantify a total of 11 plant growth regulators, including the recognized phytohormones, in grape pericarp and seed. The established method showed satisfactory precision (RSD &lt; 11.3%) and linearity (R2 &gt; 0.9980). The limits of detection (LOD) and the limit of quantification (LOQ) were 0.001–0.75 ng/mL and 0.004–2.5 ng/mL, respectively. The recovery for the three levels of analytes spiked ranged from 63% to 118%, and the matrix effect was between 73% and 119%. Finally, the proposed method was applied to investigate the dynamic hormone concentration in Vitis vinifera L. cv. Cabernet Sauvignon berries from different vineyards, and assess the changes in endogenous hormones in grapes after treatment with exogenous growth regulators. We found that the contents of IP, ABA and IAA in pericarp and IP, IAA, IBA and SA in seed were significantly down-regulated after 10 days of treatment with NAA concentrations of 10 mg/L and 40 mg/L. In conclusion, this method helps to elucidate the role played by phytohormones in the maturation process and the accumulation of quality-related metabolites in phenol-rich fruits.

Methods in food defence: a simple and robust screening for 16 rodenticides by LC-DAD/FLD following QuEChERS–based extraction

Fortunately, the intentional contamination of food or water supplies out of criminal or terroristic motivation is a rather rare event. However, in the face of asymmetric warfare and as the consequences of such an event would be severe, food defence as a necessary supplement to food safety is gaining increased attention. While some progress has been made in developing non-target detection devices, the contamination of food or water supplies using readily available rodenticides may still be revealed only by complex analytical techniques. The presented study therefore aimed to develop a quick and easy screening method for the detection of sixteen globally common rodenticides in foodstuffs. Robust operation with limited personnel and analytical resources were one benchmark to be met by the method, which uses a slightly modified QuEChERS (quick, easy, cheap, effective, rugged, safe) protocol for dispersive solid-phase extraction and subsequent ion-pair chromatography with diode-array and fluorescence detection. Quantification limits were as low as 5 µg/kg with satisfying bias (recovery) and repeatability rates of 77 to 117% and 1.8 to 17.1%, respectively. The developed method provides reliable and robust detection of these deadly poisons at toxic concentrations, which was demonstrated impressively in an improvised assault scenario.