Chlorogenic acid (CQA), the ester of caffeic acid with quinic acid, has been one of the most studied polyphenols due to its potential biological activity and usefulness in pharmaceutical treatment. We found that in an aqueous solution of each chlorogenic acid isomer, 3-, 4- and 5-CQA, its two complexes with water are formed. In the RP chromatographic system, these CQA-water derivatives differ in retention data from that of their precursors and do not decompose, which indicates their considerable stability. The formation of CQA-water complexes has not been reported yet. Comprehensive NMR research of CQA-water derivatives complexes shows that their significant stability results from the formation of hydrogen bonds between water and CQA isomer – e.g., between water and OH3, OH4 and ester groups of CQA molecule in the case of 5-CQA-water derivative. The existence of CQA-water derivatives in CQA containing food products was in the paper shown. It should be noted that the stable CQA-water complexes may exhibit a different biological activity than CQA. This issue requires separate biomedical research.

Separation of water-soluble lignins from lignocellulosic biomass provides a new and still poorly exploited feedstock to increase the sustainability of biorefineries. We applied derivatization followed by a reductive cleavage (DFRC) method, 2D-HSQC-NMR, and ³¹PNMR after ³¹P-labeling, to investigate molecular composition in water-soluble lignins obtained by alkaline oxidation from three biomass materials for energy (miscanthus, giant reed and an industrially pre-treated giant reed). Chromatographic identification of lignin products cleaved by DFRC showed a large predominance of guaiacyl (G) units in all biomasses and a lesser abundance of syringyl (S) and p-coumaryl (P) monomers. Our S/G ratios disagree with those reported in literature by other lignin separation methods. Carboxyl functions (ferulic and pcoumaric acids) were revealed by heterocorrelated ¹H–¹³C HSQC-NMR, and confirmed by ³¹P-NMR spectra of ³¹ P-labeled lignin molecules. An understanding of molecular composition of water-soluble lignins from biomass sources for energy is essential for lignin most efficient exploitation in either industrial or agricultural applications.

A nuclear magnetic resonance (NMR) method was developed to quantify cations in mineral water. The procedure was based on integration of signals from metal-ethylenediaminetetraacetic acid (EDTA) complexes at δ 2.70ppm for Mg2+ and δ 2.56ppm for Ca2+. The limits of detection were below 0.5mg/L. Lack of precision did not exceed 5%. Linearity was between 1 and 500mg/L. Correlation between NMR and a reference chromatographic method was significant (p<0.0001, R2=0.99). PLS models were also established to estimate Na+ and K+ contents. R2 was 0.85 and 0.83, respectively. Root mean square errors of cross validation (RMSECV) were 8.0mg/L and 1.9mg/L for Na+ and K+, respectively. The method was applied successfully for the analysis of 31 mineral water samples. This method is a useful tool for quantification of important cations in mineral water and might easily be adapted to other food matrices.

A rapid planar chromatographic method for identification and quantification of 25 water-soluble dyes in food was developed. In a horizontal developing chamber, the chromatographic separation on silica gel 60F(254) high-performance thin-layer chromatography plates took 12 min for 40 runs in parallel, using 8 mL ethyl acetate-methanol-water-acetic acid (65 + 23 + 11 + 1, v/v/v/v) mobile phase up to a migration distance of 50 mm. However, the total analysis time, inclusive of application and evaluation, took 60 min for 40 runs. Thus, the overall time/run can be calculated as 1.5 min with a solvent consumption of 200 μL. A sample throughput of 1000 runs/8 h day can be reached by switching between the working stations (application, development, and evaluation) in a 20 min interval, which triples the analysis throughput. Densitometry was performed by absorption measurement using the multiwavelength scan mode in the UV and visible ranges. Repeatabilities [relative standard deviation (RSD), 4 determinations] at the first or second calibration level showed precisions of mostly <or=2.7%, ranging between 0.2 and 5.2%. Correlation coefficient values (R >= 0.9987) and RSD values (<or=4.2%) of the calibration curves were highly satisfactory using classical quantification. However, digital evaluation of the plate image was also used for quantification, which resulted in RSD values of the calibration curves of mostly <or=3.0%, except for two <or=6.0%. The method was applied for the analysis of some energy drinks and bakery ink formulations, directly applied after dilution. By recording of absorbance spectra in the visible range, the identities of the dyes found in the samples were ascertained by comparison with the respective standard bands (correlation coefficients >or= 0.9996). If necessary for confirmation, online mass spectra were recorded within a minute.

Triazole fungicides are systemic fungicides applied to protect crops from fungus infections. Its use must be controlled due to the potential harmful effects in environment and human health. Before determination with a chromatographic system, analyte must be isolated and preconcentrated with an extraction step. This review presents the most used microextraction techniques for those compounds in water and several food matrices, mainly solid phase microextraction (SPME) and liquid phase microextraction (LPME) procedures. The most relevant analytical parameters of some studies from the recent literature are collected and also some advantages and disadvantages comparing SPME and LPME procedures are presented.

Multifunctional polymeric microspheres were prepared using hyper-cross-linking chemistry combined with surface-initiated atom transfer radical polymerization. The synthesized microspheres exhibited good water dispersibility, a high surface area, and pH/thermo dual-responsiveness. Fluoroquinolones (FQs), which contains a hydrophilic piperazine ring and hydrophobic fluorine atoms, were used as target analytes to assess the performance of the microspheres as a sorbent for dispersive solid-phase extraction (d-SPE). The d-SPE experimental parameters, including extraction time, amount of microspheres, extraction temperature, and sample solution pH, as well as the desorption conditions, were systematically studied. Coupled with LCMS/MS, an analytical method for analysis of trace-level FQs in water samples was developed and validated. Under optimal conditions, linearity with correlation coefficients (r) of >0.99 was achieved in the concentration range of 0.02–10 μg L−1. The limits of detection and quantification for the selected FQs were 5.0–6.7 and 12–20 ng L−1, respectively. High recovery values (93.1%–97.2%), a high enrichment factor (˜180), and good precision (RSD < 8%, n = 6) were obtained for FQ determination in spiked purified water samples. It was proposed that hydrophilic–hydrophobic transition induced by stretching and shrinking of polymer chains under different pH and temperature conditions offered good control of the surface wettability and altered the extraction behavior. The developed method was validated and was successfully applied to the analysis of FQs in environmental water samples, meat and milk samples. These results demonstrated that the water-dispersible polymeric microspheres have good potential for use in separation and extraction techniques.

The expanding demands of consumers requires food quality control to be improved all the time. Higher concentration of biogenic amines can lead to food toxicity, for example they can cause migraine headaches in people who consume products rich of serotonin or tyramine. Methylxanthines (caffeine and metabolites) can also have side effects to human comfort – high doses can lead to unrest, irritation or insomnia. Most vitamins are supplied to humans only as a part of food meals or dietary supplements. Knowledge about their concentration in food can be useful for composing various diets. In this work specification of complete sample preparation parameters for extraction of the compounds from food matrices has been reviewed. Particular attention was given to the preparation stage as well as to extraction methods that have been used. The second part of the work presents data from chromatographic methods for determination and separation of selected biogenic amines, methylxanthines and water-soluble vitamins in food. Stationary and mobile phases, detection methods as well as validation data have been reviewed. This publication is a comprehensive compendium of analytical procedures for food analyses of the previously mentioned compounds.

Pesticide residues in human milk and environmental samples from Kafr El-Zayat Governorate in Egypt were analyzed. This governorate is located near one of the biggest pesticide factories in Egypt. Organochlorine and organophosphorus pesticides were monitored, including those that have been prohibited from use in Egypt. Human milk samples (31 samples) from Kafr El-Zayat were compared with 11 samples collected from Cairo. Data were compared with results from studies performed in 1987 and 1990. The present study showed that aldrin and dieldrin, heptachlor and heptachlor epoxide, and endrin residues have been eliminated from human milk. Estimated daily intakes (EDIs) of DDT complex and gamma-HCH by breast-fed infants in Kafr El-Zayat were 85.96 and 3.1% of respective acceptable daily intakes (ADIs). beta-HCH residues showed an increasing pattern, especially in human milk samples from Cairo. DDT complex and HCH isomers in orange, spinach, lettuce, potatoes, and clover samples ranged from undetectable to very low concentrations. Higher levels of DDT and HCH were detected, but aldrin, dieldrin endrin, and the heptachlors were not detected in food of animal origin. Residues in fish samples were below maximum residue limits established by some developed countries. Those in animal milk samples approached the extraneous residue limits of the Codex Committee on Pesticide Residues. HCH residues in soil were negligible, but DDT residues in soil were somewhat higher. Among water samples, groundwater samples had the highest residues of HCHs and DDTs, followed by Nile River water and then tap water. However, the organochlorine pesticide residues were found at concentrations below the maximum allowable limits set by the World Health Organization for drinking water. Among 12 organophosphorus pesticides monitored as parent compounds, dimethoate, malathion, methamidophos, and chlorpyrifos residues were detected in low concentrations in soil samples from a pesticide factory. No organophosphorus pesticide residues were found in plant samples, except for very low residues of dimethoate in an orange sample. Water samples were devoid of organophosphorus residues as parent compounds.

MSc (Chemistry) | Department of Chemistry | Antibiotics and perfluoroalkyl substances (PFAS) are groups of anthropogenic substances that are found in industries and consumer products, i.e., antibiotics are used in healthcare facilities, pharmaceutical companies, and agriculture, whereas PFAS are used in industries and households. These compounds find their way into the environment through emission, landfill disposal, agricultural run-offs, irrigations, leaching and wastewater spillage. Their residues are widely detected in almost every environmental compartment. Their detection in drinking water and food is one of the global concerns. Their effect in living organisms have been widely documented ranging from allergic reaction to carcinogenic effect, and in serious situations they can lead to death. In this project, the background review on the behaviour of antibiotics and PFAS in different environments are discussed in chapter two. This has been done by looking into their physico-chemical properties, distribution pathways, accumulation and toxicity in various environmental compartments through available literature. After understanding their behaviour in the environment two review papers, namely Paper I and Paper II, were written. Paper I was a book chapter which focused on the application of miniaturised liquid phase extraction techniques used for extraction of antibiotics in environmental water samples. In this book chapter, the use of liquid-liquid extraction techniques was discussed and the evolution of liquid-liquid extraction technique into miniaturised extraction technique was reviewed. Paper II was a critical review which focuses on the application of dispersive liquid-liquid micro-extraction of PFAS in different environmental samples. In this paper, the principles of dispersive liquid-liquid micro-extraction was explained. Later, its application for pre-concentration of PFAS was reviewed and the future trends were discussed. In chapter four, three lab-based papers, namely Paper III, Paper IV and Paper V, were written. In Paper III, for the first time a dispersive liquid-liquid microextraction technique was developed and applied for extraction of multi-class antibiotics in macadamia nuts prior to UHPLC-qToF-MS analysis. In paper IV, a novel deep eutectic solvent was synthesised and characterised using FTIR spectroscopy. For the first time the synthesised deep eutectic solvent was applied for extraction of multiclass antibiotics in green beans prior to UHPLC-qToF-MS analysis. In Paper V, for the first a dispersive liquid-liquid micro-extraction technique was developed and applied for extraction of PFAS in food contact materials prior to UHPLC-qToF-MS analysis. Owing to their ease of operation, efficiency and sensitivity, these techniques can also be applied for preconcentration of antibiotics and PFAS in different food, environmental and biological samples. | NRF

The aim of this study was to compare the transfer of primary aromatic amines (PAAs) from napkins into cold water extract (CWE) with transfer into four different food matrices. An HPLC-MS/MS multi-analyte method for quantification of 26 PAAs in CWE was validated and applied. In addition, the method was validated for seven different PAAs in four different food matrices (cucumber, rice, pickled gherkin and butter cookie) representing wet, dry, acidic and fatty food. The CWEs of 12 coloured napkin samples were analysed, and 3 napkins released more than 0.01 mg kg-1 PAAs into the CWE. These three napkins were chosen for transfer testing with food samples. In total, seven different PAAs were quantified in the food samples. Results show that the transfer of the tested PAAs into the CWE is in most cases comparable to the transfer into the tested food samples. In some cases, the CWE overestimates transfer into food, except for the transfer of aniline into pickled gherkin, where the CWE underestimates transfer. Therefore, the CWE serves as an adequate and certainly not overestimating simulation of reality for the tested transfer of PAAs into the food samples.