This work focuses on optimization and application of voltammetric methods for determination of 5-nitroquinoline in model samples of drinking and river water using carbon film electrode (CFE). The advantages of carbon film electrode are primarily its wide potential window in both cathodic and anodic regions and also low environmental stress compared to mercury electrodes. In this contribution, CV and AdSV were used to observe electrochemical processes. For determination of 5-nitroquinoline DPV and FIA were used. Solid phase extraction was investigated as a method for preliminary separation and preconcentration for DPV. Determination of 5-nitroquinoline at CFE is based on cathodic reduction of nitrogroup. This work demonstrates the application of carbon film electrode for determination of 5-nitroquinoline in submicromolar concentrations in model samples of water.

Lipidomics as a part of metabolomics is a fast-growing area of research due to the improvement in analytical techniques. This master thesis is focused on lipid extraction techniques optimization, using liquid liquid extraction and solid phase extraction as pre-separation methods and ultra performance liquid chromatography coupled with mass spectrometry for extraction and subsequent identification of branched-chain fatty acid esters (FAHFA - branched-chain Fatty Acid esters of Hydroxy Fatty Acids). This newly discovered class of lipid molecules is associated with insulin secretion, which could improve whole body and local glucose metabolism, providing potential for diabetes 2 type treatment. Solid phase extraction of biological samples was optimized on columns regarding to sorbent composition using reversed phase columns with modified styrene divinylbenzene polymer or octadecyl-bonded polymer and normal phase columns packed with silica gel. Column Strata SI-1 Silica was the most effective for FAHFA separation from biological samples. Chromatographic separation of FAHFA was performed on UPLC Ultimate 3000 RSLC equipped with Kinetex C18 1,7 µm, 2,1 x 150 mm column using gradient program. UPLC was coupled to QTRAP 5500/SelexION, a hybrid, triple quadrupole, linear ion trap mass spectrometer equipped...

In this doctoral thesis, a novel method for the determination of primary bile acids cholic acid and chenodeoxycholic acid is presented. Bile acids play various vital roles in the mammalian body. Moreover, their determination is extremely helpful in liver and biliary disease diagnosis and management. These saturated organic compounds lack strong chromophores and fluorophores in their structure, and thus are usually hard to detect in spectroscopy. For this reason, either instrumentally advanced but expensive methods, such as mass spectrometry, or less reliable enzymatic methods are commonly employed in bile acids quantitation. Hence, the demand for simple and reliable methods for their determination is strong. Bile acids are also known to be virtually inert for direct electrochemical oxidation. Herein, a simple method for their chemical activation for electrochemical oxidation on bare electrode materials was developed, optimized and applied to cholic acid and chenodeoxycholic acid determination. The activation is based on a dehydration reaction of a primary bile acid with 0.1 mol L-1 HClO4 in acetonitrile (water content 0.55%) that introduces double bond(s) into the originally fully saturated steroid core. This naturally increases the electron density in the structure, and thus allows electrochemical...

A solid phase extraction (SPE) method was developed for simultaneous extraction of dicarboxylic acids and diols formed during hydrolysis of poly(butylene succinate), PBS, and poly(butylene adipate), PBA. The developed SPE method and subsequent GC-MS analysis were used to extract, identify and quantify low molecular weight products migrating from linear and branched poly(butylene adipate) (PBA) and poly(butylene succinate) (PBS) during aging in aqueous media. The combination of SPE and GC-MS proved to be a sensitive tool, able to detect small differences in the degradation rate during early stages of hydrolysis before any significant differences were observed by weight loss and molecular weight measurements. The detected low molecular weight products included monomers i.e. adipic acid and 1,4-butanediol for the PBA polymers and succinic acid and 1,4-butanediol for PBS. Several dimers and trimers i.e. hydroxybutyl adipate, hydroxybutyl succinate, di(hydroxybutyl) adipate, di(hydroxybutyl) succinate and hydroxybutyl disuccinate were also detected. Best extraction efficiency for 1,4-butanediol and succinic acid was achieved with a hydroxylated polystyrene-divinylbenzene resin as solid phase. Linear range for the extracted analytes was 1-500 ng/ml for adipic acid and 2-500 ng/ml for 1,4-butanediol and succinic acid. Detection and quantification limits for all analytes were between 1-2 ng/ml (S/N=3) and 2-7 ng/ml (S/N=10) respectively. Relative standard deviations were between 3 % and 7 %. Comparison of measured weight loss and the amount of monomeric products showed that weight loss during early stages of hydrolysis was mainly caused by the release of water-soluble oligomers that on prolonged ageing were further hydrolyzed to monomeric species. Significant differences in degradation rate could be assigned to degree of branching, molecular weight, aging temperature and degradation medium. Linear and branched PBA was mixed with PVC in solution cast films to study the effects of molecular weight and branching on plasticizer efficiency. Used as polymeric plasticizer, PBA formed a semi-miscible two-phase system with PVC where the amorphous part exhibited one single glass transition temperature and the degree of polyester crystallinity was dependent on molecular weight, degree of branching and blend composition. Plasticizing efficiency was favored by higher degree of branching and a 40 weight-percent polyester composition. / QC 20101209

The concept of integrated sensors in the Biotage® Extrahera™ system to perform live-monitoring of pressure inside SPE-columns is investigated. A test-rig containing the components necessary to simulate the pressure-cycle in the system is constructed and a printed-circuit board assembly is designed and implemented into its 24-column format. Liquid samples with varying viscosity are then synthesized using water and glycerol, which are used in a simplified 2-step SPE-process during which the pressure inside the columns is logged. The results obtained showed that the concept is viable and methods for clog detection as well as state assessment are discussed. However, it was established that the solution needs further testing involving complete SPE-processes with real samples before any detailed algorithms can be presented. A pre-study is finally done regarding solutions for minimizing the design to allow for implementation into the system's more spatially restricted 96-column format.

Emerging contaminants represent newly identified organic chemical pollutants that are not yet covered by routine monitoring and regulatory programs. Current research on these contaminants is greatly hindered by the shortage of analytical methods due to the complex matrices, extremely low concentration and their “emerging” nature. In this study the innovative analytical and monitoring methods have been developed and validated for determination of emerging pollutants in water (including pharmaceutical and personal care products, pesticides and artificial sweeteners) based on graphene-silica composite as the solid-phase extraction (SPE) sorbent and as the receiving phase in passive sampler. Graphene, a new allotropic member in the carbon family, has been considered to be a promising candidate for sorption material with high loading capacity because of its ultra-high specific surface area and large delocalized π-electron-rich structure. The composite employed in this work was synthesized by using the cross-link agent to covalently combine carboxylic acid groups of graphene-oxide with the amino groups of the modified silica gel. Afterwards, graphene-silica composite was obtained after treated with hydrothermal reaction in the microwave autoclave, which was demonstrated by X-ray diffraction (XRD). The analytical procedure entails SPE followed by high performance liquid chromatography equipped with tandem mass spectrometers (HPLC-MS/MS). Several crucial parameters were optimized to improve recovery of the analytes, including the amount of sorbents, the ratio of graphene oxide/amino-silica and pH value of water samples. The best recovery results were achieved with 100 mg 10 % (w/w) graphene-silica composite, which were over 70 % except four artificial sweeteners, ranitidine and triclosan. Compared with its commercial counterpart Oasis HLB, pH value variation of water samples has less effect on the recoveries, making graphene composite to be a potential receiving phase of monitoring tool. The batch-to-batch reproducibility was verified on six independently SPE cartridges with graphene-silica composites from two repeatable synthetic batches, showing relative standard deviations (RSDs) in the range of 8.3 % to 19.1 %, except ibuprofen and saccharin. The cartridges proved to be reusable for at least 10 times consecutive extractions, with RSD < 14.9 %, except ibuprofen and diclofenac. The Chemcatcher® passive sampler is frequently used for monitoring polar organic chemicals in surface water. Uptake kinetics is necessary to be quantified to calculate time-weighted average (TWA) concentration. A series of calibration experiments were conducted in the beaker renewal experiments as well as in the flow-through system with styrenedivinylbenzene-cross connect (SDB-XC) disks and graphene-silica composite as the receiving phase. The results obtained from the beaker renewal experiments showed that the uptake kinetics of accumulated compounds with all Chemcatcher® configurations can keep linear within 2 weeks. The innovative configuration using graphene-silica composite powder placed between two PES membranes was able to accumulate eleven of the selected compounds with uptake rate (Rs) from 0.01 L/day (acesulfame K and sucralose) to 0.08 L/day (chlothianidin), while its commercial counterpart SDB-XC disks with polyethersulfone (PES) membranes can accumulate seven substances with Rs from 0.02 L/day (sucralose and chlothianidin) to 0.15 L/day (carbamazepine). In the flow-through system, when Chemcatchers® were equipped with SDB-XC disks without PES membranes, the linear uptake range for the majority of compounds was only in one week, except atrazine. The Rs of accumulated compounds were from 0.16 L/day (chloramphenicol) to 1.04 L/day (metoprolol) that are higher than the same substances in the beaker renewal experiments, in which the Rs of chloramphenicol and metoprolol were 0.09 L/day and 0.56 L/day respectively. However, if the PES membranes were employed, the uptake kinetics in both calibration experimental designs were comparable: the Rs of accumulated compounds from the configuration with SDB-XC disks covered by PES membranes were from 0.035 L/day (sucralose) to 0.17 L/day (carbamazepine) and from the configuration with graphene-silica composite were from 0.01 L/day (gemfibrozil) to 0.08 L/day (chlothianidin). Moreover, the uptake range can keep linear within two weeks. The developed Chemcatcher® method was successfully applied in real surface waters. 1-H benzontriazole, tolyltriazole and caffeine were the main contaminants in Elbe River and the Saidenbach drinking water reservoir. The investigated results between summer and autumn monitoring period were not significantly different.:Acknowledgement I Abstract III Zusammenfassung V Content IX List of Figures XIII List of Tables XVII Table of Abbreviations XIX 1. Motivation 1 2. Introduction 3 2.1 Emerging contaminants 3 2.1.1 Definition 3 2.1.2 Sources 3 2.1.3 Concern about the adverse impacts 5 2.2 Analysis of the emerging contaminants 7 2.2.1 General analytical process 7 2.2.2 Enrichment techniques 8 2.2.2.1 Liquid-liquid extraction (LLE) 8 2.2.2.2 Solid-phase extraction (SPE) 9 2.2.2.3 Innovative type of solid-phase extraction 13 2.2.3 Analytical methods 15 2.3 Graphene and its application in analytical chemistry 19 2.3.1 Introduction 19 2.3.2 Synthesis methods of graphene 20 2.3.3 Application in sample pre-treatment 21 2.3.3.1 Graphene-based material as SPE sorbent 21 2.3.3.2 Graphene-coated fibers as SPME sorbent 22 2.3.3.3 Magnetic graphene as MSPE sorbent 23 2.3.3.4 Graphene-based MIPs 24 2.4 Chemcatcher®—a passive sampling technique 25 2.4.1 Introduction 25 2.4.2 Theory 26 2.4.2.1 Equilibrium passive sampling 27 2.4.2.2 Kinetic passive sampling 28 2.4.3 Concept of Chemcatcher® 28 2.4.4 Calibration of Chemcatcher® 33 2.4.5 Performance and reference compounds 36 3. Study objectives and hypotheses 39 3.1 Study objectives 39 3.2 Hypotheses 41 4. Material and methods 43 4.1 Materials 43 4.1.1 Chemicals and solutions 43 4.1.2 Consumable materials and instruments 44 4.2 Synthesis of graphene-silica composite 46 4.3 SPE experiments 49 4.3.1 Packing method 49 4.3.2 SPE procedure 49 4.3.3 Optimization of SPE procedures 51 4.3.4 Repeatability and reusability test 52 4.4 Chemcatcher® experiments 53 4.4.1 Preparation and precondition 53 4.4.2 Calibration of Chemcatcher® 55 4.4.2.1 Preliminary test 55 4.4.2.2 Experimental design of the beaker batch tests 56 4.4.2.3 Experimental design of the flow-through system 57 4.4.3 Monitoring application of Chemcatcher® in surface water 59 4.4.4 Elution process 60 4.4.5 Statistic data evaluation 61 4.5 HPLC-MS/MS analysis 62 5. Results and discussion 63 5.1 Preparation and characterization of graphene-silica composite 63 5.2 SPE performance of the graphene-silica composite 67 5.2.1 Preliminary test of packing methods 67 5.2.2 Optimization of SPE procedures 68 5.2.2.1 The amount of sorbent 68 5.2.2.2 Graphene ratio in the composites 68 5.2.2.3 pH value of the water sample 69 5.2.3 Repeatability and reusability test 72 5.2.3.1 Performance of the off-line SPE 72 5.2.3.2 Repeatability and reusability test results 75 5.2.4 Summarized discussion of the SPE performance 76 5.3 Calibrating results of Chemcatcher® 86 5.3.1 Pre-test results 86 5.3.1.1 Feasibility test of commercial disks as receiving phase 86 5.3.1.2 Stability test 88 5.3.1.3 Elution optimization. 88 5.3.1.4 Recovery of the filters 92 5.3.2 Calibration results of renewal experiments 93 5.3.2.1 SDB-XC disks without and with membranes 93 5.3.2.2 Graphene-silica composite as receiving phase 97 5.3.3 Calibration results of the flow-through system experiments 101 5.3.3.1 Determination of experimental parameters 101 5.3.3.2 Concentration control 103 5.3.3.3 Calibration results 105 5.3.3.4 Preliminary evaluation of performance and reference compounds 112 5.4 Application of Chemcatcher® in surface water 114 5.5 Discussion about problems of commercial disks as receiving phase in Chemcatcher® 118 5.5.1 Deformation of commercial disks 118 5.5.2 The particles in the solution after elution 119 6. Conclusion and perspective 121 7. Annex 125 7.1 Material and methods 125 7.1.1 Chemicals 125 7.1.2 Silica gel and graphene oxide 144 7.1.3 Microwave reduction program 144 7.1.4 Working schedule of the calibration experiments in flow-through system 144 7.1.5 HPLC-MS/MS conditions 146 7.2 Experimental results 149 7.2.1 Stability of the colloid solution of graphene oxide 149 7.2.2 EDX analysis results 149 7.2.3 HPLC-MS/MS results 152 7.2.4 Calibrating results of the beaker renewal experiment 153 7.2.5 Calibrating results of the flow-through system experiments 157 7.2.6 Monitoring results in the Elbe River 161 Reference 163

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[pt] O objetivo da pesquisa foi dedicado à preparação de novos materiais híbridos à base de sílica contendo sistemas moleculares ou nanométricos de carbono com sistema de elétrons pi conjugados, imobilizados covalentemente para posterior aplicações como adsorventes e eletrodos para pré-concentração e determinação de compostos aromáticos. Deste modo, propôs-se o desenvolvimento das metodologias para as imobilizações covalentes de antraceno (Ant), pontos quânticos de óxido de grafeno (GOQDs) e nanopontos de carbono (CDs) na superfície da sílica (SiO2). Estes compostos são constituídos de sistemas conjugados de elétrons pi e, portanto, podem formar interação intramolecular de empilhamento pi–pi com compostos aromáticos. Nanocompósito de GOQDs imobilizados foi preparado através da interação covalente de fragmentos nanoméricos de óxido de grafeno (GO). Três tipos de SiO2-Ant foram obtidos através de abordagem de montagem da superfície pela reação de alquilação condensação de sílica modificada com grupos aminopropila. Estes materiais podem ter diferentes arranjos de ligantes de antraceno na superfície da sílica e, portanto, podem apresentar diferentes propriedades doadoras de elétrons-pi. Nanocompósitos de sílica gel com CDs imobilizados foram preparados por duas abordagens diferentes. Na primeira, os CDs foram obtidos a partir do ácido cítrico como material de partida e posteriormente imobilizados em sílica. O segundo método consistiu no uso de sílica gel porosa como nanorreator para a preparação de CDs. Este método é simples e robusto, o qual permite um maior controle do tamanho e da composição do nanomaterial. Além disso, os efeitos da modificação da sílica, tamanho dos poros, tempo de síntese, estabilidade hidrolítica, tamanho das nanopartículas de carbono e rendimento quântico da fluorescência foram avaliados. Foi demonstrado que a carbonização do gel aminosilica com ácido cítrico incorporado resultou na formação de CDs não imobilizados e CDs imobilizados. Devido à forte fixação na superfície, os CDs podem ser facilmente purificados através de simples lavagem do nanocompósito com água. Os C-pontos preparados apresentaram fotoluminescência independente de excitação a 445 nm com rendimento quântico até 80 porcento, o que os tornam atraentes para aplicação bioanalítica. O nanocompósito imobilizado com GOQDs foi preparado por ligações covalentes dos fragmentos de GO em nanoescala. A composição da camada superficial de todos adsorventes foi determinada a partir de análises elementares e termogravimétricas, fotoelétrons de raios X, ressonância magnética nuclear no estado sólido, Raman, FTIR e espectroscopia de fluorescência. As propriedades texturais dos adsorventes foram determinadas, bem como a cinética de imobilização do ligante, o grau de transformação da superfície e a estabilidade hidrolítica dos grupos enxertados, o efeito da porosidade da sílica no grau de conversão do ligante. As propriedades de adsorção dos materiais foram avaliados pela extração em fáse sólida nos modos dinâmico e estático para os compostos modelos azul de metileno e antraceno em várias fases móveis aquosas-orgânicas e orgânicas, na presença de componentes interferentes. Os nanomateriais obtidos apresentaram maior afinidade para compostos aromáticos do que os cartuchos comerciais C18 para extração em fase sólida (SPE) de fases orgânicas móveis que permitem a separação em uma etapa dos hidrocarbonetos aromáticos policíclicos (PAHs) na matriz com alta concentração de ácidos graxos. Ademais, sílica gel com GOQDs imobilizados foi usado para análise eletroquímica de antibióticos e hormônios selecionados. O eletrodo demonstrou atividade eletrocatalítica em relação ao estriol (ET), dietilestilbestrol (DES), sulfametoxazol (SMZ) e trimetoprim (TMP) que possibilitaram determinar esses analitos com até 0.009 μmol L(-1) (ET). / [en] The objective of the present research was devoted to the preparation of new silica-based hybrid materials having covalently immobilized carbon-containing molecular and nanometric systems with delocalized pi-electrons that can be used as adsorbents and electrodes for preconcentration and determination of aromatic compounds. For this purpose, methodologies for covalent immobilization of anthracene (Ant), graphene oxide quantum dotes (GOQDs) and carbon nanodots (CDs) on silica surface (SiO2) have been developed. These compounds have a conjugated system of pi-electrons and thus can form intramolecular pi–pi stacking interaction with aromatic compounds. The nanocomposite with immobilized GOQDs was prepared by covalent immobilization of nanoscale graphene oxide (GO) fragments. Three sets of SiO2-Ant were obtained using reaction surface assembling reactions by alkylation and condensation of silica with immobilized primary amines. These materials can have different arrangements of anthracene ligands on silica surface and so pi-donor properties. Silica gel nanocomposites with immobilized CDs were prepared by two different approaches. For the first one, the CDs were obtained from the molecular precursor and then immobilized on silica. For the second method, CDs were prepared by nanoreactor approach directly in silica gel pores. The second method is facile and robust and also allows better control of the particle size and composition. The effects of silica gel modification, pore size, synthesis time, hydrolytic stability, carbon nanoparticle size and quantum yield of the fluorescence were studied. It was demonstrated that the carbonization of aminosilica gel with embedded citric acid resulted in the formation of unbound CDs and immobilized CDs. Due to firm attachment to the surface CDs can be easily separated from low-molecular-weight impurities and CDs by simple rinsing of the nanocomposite with water. As prepared CDs demonstrate excitation-independent photoluminescence at 445 nm with quantum yield up to 80 percent that makes them attractive for bioanalytical application. The composition of the surface layer of the adsorbents was determined from elemental and thermogravimetric analysis, X-ray photoelectron, solid nuclear magnetic resonance, Raman, FTIR, and fluorescent spectroscopy. The textural properties of the adsorbents were determined as well as ligand immobilization kinetics, the degree of surface transformation and hydrolytic stability of the grafted groups, the effect of silica porosity on ligand conversion degree. The adsorption properties of the materials were studied in dynamic and static solid-phase extraction (SPE) modes for the model compounds methylene blue and anthracene in various aqueous-organic and organic mobile phases, in the presence of interfering components. It was demonstrated that studied materials have a higher affinity towards aromatic compounds than commercial C18 SPE cartridges in organic mobile phases that allow one-step separation of polycyclic aromatic hydrocarbons in the matrix with a high concentration of fatty acids. Also, silica-immobilized GOQDs was used for electrochemical analysis of selected antibiotics and hormones. The electrode demonstrated electrocatalytic activity towards estriol (ET), diethylstilbestrol (DES), sulfamethoxazole (SMZ), and trimethoprim (TMP) that made it possible to determine these analytes with up to 9 nmol L(-1) (ET).

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