Magdalena Śliwka-Kaszyńska

Calixarenes as Stationary Phases in High Performance Liquid Chromatography

Calixarenes are a class of host molecules with three-dimensional cavity capable of accepting guest molecules. The interest of calixarenes in analytical and separation chemistry has increased in recent years because of their ability to form reversible complexes with both neutral and charged molecules. Calixarenes have been utilized in gas chromatography, solid-phase extraction, capillary electrophoresis and overall in high performance liquid chromatography. This short review is focused on recent advances in synthesis and characterization of calixarene, calixresorcinarene and calixpyrrole stationary phases, chemically bonded or dynamically adsorbed onto silica gel or used as mobile phase additives, and its application to separation of organic and inorganic solutes by high performance liquid chromatography.

1,3-Alternate 25,27-dibenzoiloxy-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel as a new type of HPLC stationary phase.

A new 1,3-alternate 25,27-dibenzoiloxy-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel stationary phase (1,3-Alt CalixBn) has been prepared and used for the separation of aromatic positional isomers by high-performance liquid chromatography (HPLC). The effect of organic modifier content and pH of the mobile phase on retention and selectivity of these compounds were studied. Application examples were provided for separation of purine and pyrimidine bases and non-steroidal anti-inflammatory drugs.

Elucidation of transformation pathway of ketoprofen, ibuprofen, and furosemide in surface water and their occurrence in the aqueous environment using UHPLC-QTOF-MS

AbstractThe identification and determination of transformation products (TPs) of pharmaceuticals is essential nowadays, in order to track their fate in the aqueous environment and, thus, to estimate the actual pollution. However, this is a challenging task due to the necessity to apply high-resolution instruments enable to detect known and unknown compounds. This work presents the use of liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) as a powerful tool for the identification of three selected pharmaceuticals, furosemide (FUR), ibuprofen (IBP), and ketoprofen (KET), and their TPs in various water samples. Laboratory degradation experiments were performed using xenon lamp as a source of the irradiation in order to simulate phototransformation processes which may occur in the environment. Furthermore, the photodegradation kinetics of three selected compounds were assessed in a reactor equipped with xenon lamp in river water samples. Five TPs of IBP, seven of KET, and five of FUR were identified; some of them are presented here for the first time. Accurate mass measurements and fragmentation pattern obtained during an LC-QTOF-MS analysis allowed for structure elucidation of TPs followed by the creation of transformation pathway of selected pharmaceuticals. Finally, different water samples (wastewater influent and effluent, river water, untreated and treated water) were analyzed in order to estimate the presence of parent and transformed compounds. Only KET was detected in untransformed form in considered samples. Most of the TPs of selected drugs were found at least once in all water samples. Although IBP and FUR were not present in water samples as parent compounds, their different TPs occur. A great potential of LC-QTOF-MS in the identification and structural elucidation of TPs in the environment, allowing the recognition of the fate of pharmaceuticals in the environment through the determination of transformation pathway, has been presented. Phototransformation of three selected pharmaceuticals

Polycyclic aromatic hydrocarbons as test probes to investigate the retention behavior of 1,3-alternate calix[4]arene silica-bonded stationary phases

A series of polycyclic aromatic hydrocarbons (PAHs) of different size and shape has been used to characterize the chromatographic behavior of five calix[4]arene stationary phases in 1,3-alternate conformation synthesized in our laboratory. The selection of linear, four-ring nonlinear, and five-ring PAHs gave data on selectivity changes across range of the calix[4]arene columns. Retention of the 12 aromatic solutes has been evaluated at various methanol contents in the mobile phase (70-100% v/v) and column temperatures (20-45°C). The thermodynamic parameters underlying the retention mechanisms revealed that each of the five calix[4]arene columns exhibited variation in selectivity and retention of PAHs caused by enthalpy and entropy effects. The calixarene stationary phases substituted with electron-withdrawing groups exhibit enhanced selectivity toward PAHs in comparison to the rest of the investigated columns. The observed divergences are due to differences in solute-stationary phase interactions and originate in π-π and π-electron transfer specific to the analytes and the type of calix[4]arene functionalization at the upper rim, as well as steric and sorption phenomena.

Identification and characterization of the Indian Yellow dyestuff and its degradation products in historical oil paint tube by liquid chromatography mass spectrometry

An analytical protocol for identification of dyes using reversed phase liquid chromatography-mass spectrometry with atmospheric pressure electrospray ionization (LC-ESI/MS) is presented. The developed method has been successfully applied in identification of euxanthic acid and euxanthone, the main components of the Indian Yellow dye in a historical oil paint tube produced by Richard Aines, a recognizable French company supplying art materials. The paint tube from which the sample has been taken belonged to a famous Polish painter from the 19th century – Jan Matejko. Various methods of extraction of the Indian Yellow dyestuff from the oil paint were systematically investigated. Efficiencies of the nine extraction procedures (based respectively on use of: HCl, HF, acetylacetone, and formic, tartaric, oxalic, trifluoroacetic and citric acids) were compared on the basis of euxanthic acid to euxanthone chromatographic peak areas ratio. It was found that use of HF, acetylacetone and the organic acids ensures a non-destructive recovery of intact acid-labile components, while the strong HCl mineral acid not only allowed extraction of the colorant from the binding medium, but also decomposes the glycosidic dye into the parent aglycon and causes a formation of methyl euxanthonate and numerous products which may hinder the proper identification of the dye. The Indian Yellow was fully characterized with the use of spectrochromatographic techniques for the first time. The fragmentation pathways of the identified colorant ions and their degradation products were proposed.

A multi-analytical approach to the characterization of natural organic dyestuffs and inorganic substrates present in the 19th-century artistic oil paints manufactured by a French art materials supplier Richard Ainès

This paper presents a comprehensive analysis of artistic paints produced in the 19th century by a French art materials supplier Richard Aines. Improved mild extraction with hydrofluoric acid enabled the observation of intact organic dyes. Reversed-phase liquid chromatography with diode-array and mass spectrometry detection was utilised for the identification of 35 dyes present in yellow and red paint samples, and in selected plant extracts. The developed analytical method allowed more efficient separation of several isomeric flavonoid and anthraquinone dye components of the paint samples. Persian berries and weld were identified as the dye sources in the yellow paint samples. The red oil paint had been coloured with the madder lake-type plant. Studies of dye extracts of the historical samples show the presence of uncommon dye components (quercetin-O-rhamnoside-glucuronide and rhamnasin-O-rhamnoside-glucoside) that could enhance this identification. The paint samples were additionally analyzed by X-ray fluorescence (XRF) and scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX). Aluminum, Sn, Zn, Ca, Cu, S, Si, and K were detected confirming the presence of aluminium hydrate and tin salts as carriers, as well as chalk, and other components used during the production of these paints. The SEM with the BSE detector images revealed the homogenous texture of finely ground lake pigments.

Phototransformation of Amlodipine: Degradation Kinetics and Identification of Its Photoproducts

Nowadays, monitoring focuses on the primary compounds and does not include degradation products formed during various biological and chemical processes. Transformation products may have the same effects to human health and the environment or sometimes they can be more toxic than the parent compound. Unfortunately, knowledge about the formation of degradation products is still limited, however, can be very important for the environmental risk assessment. Firstly, the photodegradation kinetic of amlodipine was investigated in two experimental conditions: during the exposure to solar radiation and during the exposure to the light emitted by the xenon lamp. In all cases degradation of amlodipine followed a pseudo-first-order kinetics. In the next step, identification of transformation products of amlodipine formed during the exposure to xenon lamp irradiation was performed using ultra high performance liquid chromatography quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS). As a result sixteen photoproducts were identified, their structures were elucidated and ultimately the transformation pathway was proposed. Fifteen compounds (out of 16 photoproducts) were newly identified and reported here for the first time; some of those compounds were formed from the first photoproduct, amlodipine pyridine derivative. Several analytes were formed only in acidic or basic conditions. Furthermore, the occurrence of amlodipine and its identified degradation products was investigated in environmental waters. Only one out of 16 compounds was found in wastewater effluent. The possibility of the sorption of examined analytes to sewage sludge particles was discussed based on QSAR.

Chromatographic and Spectroscopic Identification and Recognition of Natural Dyes, Uncommon Dyestuff Components, and Mordants: Case Study of a 16th Century Carpet with Chintamani Motifs

A multi-tool analytical practice was used for the characterisation of a 16th century carpet manufactured in Cairo. A mild extraction method with hydrofluoric acid has been evaluated in order to isolate intact flavonoids and their glycosides, anthraquinones, tannins, and indigoids from fibre samples. High-performance liquid chromatography coupled to spectroscopic and mass spectrometric detectors was used for the identification of possible marker compounds with special attention paid to natural dyes present in the historical samples. Weld, young fustic, and soluble redwood dye were identified as the dye sources in yellow thread samples. Based on the developed method, it was possible to establish that red fibres were coloured with lac dye, whereas green fibre shades were obtained with indigo and weld. Tannin-containing plant material in combination with indigo and weld were used to obtain the brown hue of the thread. Hyphenation of high-performance liquid chromatography (HPLC) with quadrupole time-of-flight mass spectrometry (QTOF MS) and triple-quadrupole mass spectrometry (QqQ MS) enabled us to recognise four uncommon and thus-far unknown dye components that were also found in the historical samples. These compounds probably represent a unique fingerprint of dyed threads manufactured in a Turkish workshop. Scanning electron microscopy with energy-dispersive X-ray detector (SEM-EDS) and Fourier transform infrared spectroscopy (FT-IR) were used for the identification and characterisation of substrates and mordants present in the historical carpet. Carbon and oxygen were detected in large quantities as a part of the wool protein. The presence of aluminium, iron, and calcium indicated their usage as mordants. Trace amounts of copper, silica, and magnesium might originate from the contaminants. FT-IR analysis showed bands characteristic for woollen fibres and SEM micrographs defined the structure of the wool.