Development and application of new polymeric materials for sorptive extraction techniques

El desenvolupament de diferents materials per a les tècniques d’extracció mitjançant processos de sorció és una àrea en continua expansió; no obstant, l’extracció d’anàlits polars encara és un tema que requereix més investigació. En aquesta Tesi s’han desenvolupa nous materials que reuneixen de selectivitat i/o capacitat característiques per a extreure contaminants orgànics polars en mostres aquoses. La primera part descriu el desenvolupament de nous materials polimèrics que milloren la capacitat i selectivitat de l’extracció en fase solida, i hi inclau els polímers altament entrecreuats amb caràcter hidrofílic, els sorbents altament entrecreuats d’intercanvi iònic de mode-mixte i els líquids iònics suportots en fases polimèriques; així com la seva avaluació com a nous sorbents per a la extracció de contaminats polars en diferents mostres aquoses mediambientals seguit de l’anàlisi per LC. La segona part está centrada en la preparació de noves barres agitadores amb recobriments monolítics polars i la seva posterior aplicació per l’extracció d’analits polars en diferents aigües de procedéncia mediambiental.The development of different materials for sorptive extraction techniques is a continuously evolving field of research. Although there have been significant developments in this area, the extraction of polar analytes is still considered the bottleneck of the extraction process. The efforts have been undertaken to improve capacity and selectivity. For this reason, one of the main objectives of this Thesis is to develop new materials to extract polar organic contaminants from water samples. The first part reports on the development of new polymeric materials for solid-phase extraction including hypercrosslinked polymers with hydrophilic character, mixed-mode ion-exchange hypercrosslinked sorbents and supported ionic liquid polymeric phases and their evaluation as SPE sorbents for the extraction of polar contaminants, followed by LC analysis. The second part is focused on the preparation of new stir bars with polar monolithic coatings and their application to stir bar sorptive extract polar analytes from environmental water samples

Hydrophilic hypercrosslinked polymeric sorbents for the solid-phase extraction of polar contaminants from water

Three new hypercrosslinked polymers with hydrophilic character arising from hydroxyl moieties in their skeletons have been prepared in microsphere format and applied to the off-line solid-phase extraction (SPE) of polar compounds from water samples. For sample volumes of 1000 ml, the recoveries of various polar pesticides, such as oxamyl, methomyl, selected phenolic compounds, as well as some pharmaceuticals, were close to 90%. The HXLPP-polar polymer with the best performance characteristics was applied to real samples. Its performance was also compared to commercially available sorbents, such as LiChrolut EN (hydrophobic, hypercrosslinked), Oasis HLB (hydrophilic, macroporous) and Isolute ENV+ (hydrophilic, hypercrosslinked); the new sorbent out-performed the commercially available sorbents. The polymer was applied successfully in off-line SPE of river water samples followed by liquid chromatography and ultraviolet detection, providing a good linear range and detection limits of 0.2 μg l-1 for the majority of the compounds, with the exception of oxamyl, methomyl, guaiacol and salicylic acid where the detection limit was 0.5 μg l-1

Synthesis and application of hypercrosslinked polymers with weak cation-exchange character for the selective extraction of basic pharmaceuticals from complex environmental water samples

The synthesis of high specific surface area sorbents (HXLPP-WCX) in the form of hypercrosslinked polymer microspheres with narrow particle size distributions, average particle diameters around 6 µm, and weak cation exchange (WCX) character, is described. The WCX character arises from carboxylic acid moieties in the polymers, derived from the comonomer methacrylic acid. A novel HXLPP-WCX sorbent with an attractive set of chemical and physical properties was then used in an off-line solid-phase extraction (SPE) protocol for the selective extraction of a group of basic compounds from complex environmental samples, a priority being the clean separation of the basic compounds of interest from acidic compounds and interferences. The separation power of the new sorbent for basic pharmaceuticals was compared to two commercially available, mixed-mode sorbents, namely Oasis WCX and Strata X-CW. Under identical experimental conditions, HXLPP-WCX was found to deliver both higher capacity and better selectivity in SPE than either of the two commercially available materials. In an optimised SPE protocol, the HXLPP-WCX sorbent gave rise to quantitative and selective extractions of low µg l-1 levels of basic pharmaceuticals present in 500 ml of river water and 250 ml of effluent waste water

An 89-year-old patient with acquired murmur associated with pulmonary embolism

Pulmonary embolism (PE) is the third most common cause of death in hospitalized patients. Diagnosis is often missed because of a non-homogeneous clinical picture. We present a case of an 89-year-old patient with an acquired murmur associated with pulmonary embolism. When examined by a family physician the patient had no symptoms typical for PE. During hospitalization, dyspnoea was exacerbated; a non-productive cough, chest pain and oliguria were observed. Pulmonary embolism was diagnosed, but because of the renal failure diagnosis was not confirmed by angio-CT

Supported ionic liquids for the efficient removal of acetylsalicylic acid from aqueous solutions

Acetylsalicylic acid, commercially available as aspirin, is one of the most used drugs in the world, being detected in several environmental compartments, including drinking water supplies. Given its environmental impact, the development of a cost‐effective technology capable of removing this pharmaceutical from water samples is of high relevance, for which materials based on silica chemically modified with ionic liquids (SILs) can be foreseen as a promising alternative. In this work, four SILs (with the chloride anion and imidazolium or tetraalkylammonium cations of different alkyl side chain length) were synthesized and characterized, and their potential for the adsorption of acetylsalicylic acid appraised by adsorption kinetics and isotherms. Envisioning their use to treat drinking water, the toxicity of all SILs towards the liver cell line Hep2G was determined. The best identified SIL, comprising the dimethylbutylammonium cation, displays a maximum adsorption capacity of 0.08 mmol/g, being 1 g of this material sufficient to treat ca. 14,500 L of water containing 1 μg/L of acetylsalicylic acid (under ideal conditions). Furthermore, this material has a negligible toxicity towards the liver cell line Hep2G. The results obtained reinforce the potential of SILs as alternative adsorbents to effectively remove a cetylsalicylic acid from aqueous solutions, and may be envisioned as a promising strategy for the treatment of wastewater and drinking water.publishe

Dispersible microporous di-block co-polymer Nanoparticles via polymerisation-induced self-assembly

Microporous materials are predominantly formed as insoluble powders which means that they can be difficult to process. Here we report a new class of solvent-dispersible porous polymers synthesised by reversible addition-fragmentation chain transfer mediated polymerisation-induced self-assembly (RAFT-mediated PISA), formed from a PEG macro-CTA polymerised with divinylbenzene and fumaronitrile. The particles have a dual morphology consisting of smaller spheres of 24-29 nm aggregated into larger particles of 204 - 262 nm. Gas sorption analysis showed the particles to have BET surface areas of 274 to 409 m2/g with internal pore sizes centred around 1.8 nm and further larger pores arising from the sphere packing of the aggregates. The particles were found to be photoluminescent (emission λmax = 326 nm) when exposed to UV light which could be quenched by the addition of nitroaromatic compounds. For example, 99% if the emission was quenched in the presence of 38 ppm of picric acid

May I?

Komuna Warszawa Your Majesty koncepcja i choreografia: Katarzyna Sikora, Marcin Miętus, muzyka: Jacek Sotomski, światło i przestrzeń: Aleksandr Prowaliński, współpraca dramaturgiczna: Maria Stokłosa, konsultacja kostiumów: Maja Skrzypek premiera: 17 listopada 202

Wpływ autooksydacji oleju rzepakowego na powstawanie melanofosfatydów

The results obtained in the present study suggest that carbonyl compound developing in the course of autoxidation of rapeseed oil react with phosphatides, which, in turn, lead to development of coloured compounds, thę so-called melanophosphatides, that reduce the quality of the phospholipids obtained from the oil.Zbadano proces powstawania melanofosfatydów w wyniku kondensacji grup aminowych fosfolipidów z aldehydami pochodzącymi z utlenionego oleju. W tym celu otrzymano fosfolipidy i oczyszczono je z substancji towarzyszących, głównie wolnych cukrów. Rafinowany olej rzepakowy poddawano procesowi utlenienia, a następnie próbki o różnej zawartości aldehydów ogrzewano w temperaturze 80 i 120°C z fosfolipidami. Wstępnie przeprowadzono reakcję fosfolipidów z aldehydem mirystynowym. Produkty reakcji badano spektrofotometrycznie w zakresie UV. Ustalono, że proces autooksydacji, który towarzyszy wszystkim etapom wydobycia i rafinacji oleju ma swój udział w powstawaniu melanofosfatydów. Podobnie jak podczas reakcji fosfolipidów z cukrami, w obecności aldehydów pochodzących z utlenionego oleju, powstają barwne związki pogarszające właściwości organoleptyczne fosfolipidów