A rapid and accurate quantitative method was developed and validated for the analysis of four urinary organic acids with nitrogen containing functional groups, formiminoglutamic acid (FIGLU), pyroglutamic acid (PYRGLU), 5-hydroxyindoleacetic acid (5-HIAA), and 2-methylhippuric acid (2-METHIP) by liquid chromatography tandem mass spectrometry (LC/MS/MS). The chromatography was developed using a weak anion-exchange amino column that provided mixed-mode retention of the analytes. The elution gradient relied on changes in mobile phase pH over a concave gradient, without the use of counter-ions or concentrated salt buffers. A simple sample preparation was used, only requiring the dilution of urine prior to instrumental analysis. The method was validated based on linearity (r2 ¡Ý 0.995), accuracy (85¨C115%), precision (C.V. < 12%), sample preparation stability (¡Ü 5%, 72h), and established patient ranges. The method was found to be both efficient and accurate for the analysis of urinary zwitterionic organic acids.

Cieľom tejto diplomovej práce je stanoviť kvalitu a zloženie medu, taktiež stanoviť jeho botanický pôvod na základe profilu sacharidov v mede. Med je prírodný produkt vysokej kvality a vďaka značnej spotrebe a nemalej trhovej hodnote je tiež terčom na falšovanie. S cieľom identifikovať podvody a cudzorodé látky, pochádzajúce z cukrových sirupov, boli analyzované oligosacharidy a polysacharidy na báze maltodextrínov. Teoretická časť popisuje chemické zloženie medu a hlavné princípy aplikovanej inštrumentálnej techniky. Poskytuje literárny prehľad existujúcich analytických metód na stanovenie sacharidov prítomných v mede a na odhalenie jeho falšovania. Boli definované hlavné body falšovania a autenticity, vrátane legislatívnych aspektov a opisu bežných druhov falšovania. Experimentálna časť obsahuje postupy, ktoré vedú k vývoju a optimalizácii chromatografických podmienok a parametrov elektrochemického detektora na stanovenie sacharidov a maltodextrínov (oligosacharidov a polysacharidov) vo vzorkách medu. Použitá analytická technika bola vysoko účinná aniónovo-výmenná chromatografia (HPAEC) spojená s pulzným amperometrickým detektorom (PAD). Vyvinutá a optimalizovaná chromatografická metóda bola taktiež validovaná z hľadiska linearity, dynamického rozsahu, analytických limitov, presnosti a správnosti. Na záver bola táto vypracovaná metóda úspešne zhodnotená analýzou autentických a falšovaných vzoriek medu rôzneho botanického pôvodu pochádzajúcich z členských štátov EÚ.

Läkemedel och per- och polyfluorerade alkylsubstanser (PFAS) har identifierats i utgående vatten från avloppsvattenverk där förekomsten av dessa mikroföroreningar har fått mycket uppmärksamhet då dessa ämnen har visats kunna leda till negativa effekter på den akvatiska miljön. De traditionella reningsteknikerna som idag används på avloppsreningsverk (ARV) har begränsad reningseffekt på mikroföroreningar där ett särskilt reningssteg för avancerad rening av mikroföroreningar krävs för att minska utsläppen av dessa till miljön.                                                              Denna studie syftade till att undersöka reduktionen av mikroföroreningar vid kombination av granulärt aktivt kol (GAK) och anjonbytare (AIX). Samt att undersöka vilken utformning, uppströmsflöde med fluidiserad bädd eller nedströmsflöde med fixerade bäddar, som fungerade mest effektivt med avseende på driftstabiliteten. Vidare syftade arbetet till att utifrån tidigare insamlade data från liknande kolonnförsök på Uppsala Vatten utreda eventuell korrelation mellan totalt organiskt kol (TOC), löst organiskt kol (DOC) och UVA med läkemedel och PFAS som skulle kunna användas som uppföljningsmetod i det senare fullskaliga reningssteget på Kungsängsverket. Kolonnförsöken bestod av sju kolonner vilka delades in i tre driftlinjer. Driftlinje ett bestod av ett GAK-filter med Cyclecarb 401 följt av ett AIX-filter med Purolite 694E, liknande utformning användes för driftlinje två men där GAK-filter med Filtrasorb 400 användes i stället för Cyclecarb 401. Samtliga filter i driftlinje ett och två drevs med nedströmsflöde. Den sista driftlinjen som undersöktes bestod av Cyclecarb 401 följt av två AIX-filter med uppströmsflöde och fluidiserade bäddar. Till varje driftlinje pumpades utgående vatten från Kungsängsverket ARV genom en förbehandling bestående av två patronfilter. I GAK- och AIX-filtren med nedströmsflöde användes en kontakttid på 15 respektive 5 minuter medan en kontakttid på 2 minuter användes för de fluidiserades AIX-filtren. Reningseffektiviteten undersöktes med avseende på PFOS, diklofenak, citalopram, metoprolol och oxazepam vid två tillfällen motsvarande 100 respektive 5 000 behandlade bäddvolymer i GAK-filtren. Utifrån analyserna beräknades reduktionsgraden över de enskilda filtren samt över varje driftlinje. Driftstabiliteten undersöktes genom att jämföra backspolningsbehovet för de tre driftlinjerna samt genom att undersöka reduktionen av TOC, DOC och UVA över dessa. Resultaten visade på god reduktion av mikroföroreningar över samtliga driftlinjer, där reduktionen var över 80 procent. Vid jämförelse av de olika GAK-filtren uppvisade Cyclecarb 401 högre reduktion av PFOS och diklofenak jämför med Filtrasorb 400. Seriedrift av GAK- och AIX-filter visades komplettera varandra där mikroföroreningar som avskildes sämre av GAK avskildes i efterföljande AIX vilket medför ett mer resurseffektivt användande av adsorbenterna. Stabiliteten med avseende på backspolningsbehov och reduktion var högst för driftlinje tre och viss korrelation mellan TOC och UVA och några mikroföroreningar kunde ses men där fler analyser skulle behövas för att undersöka detta närmare. / Pharmaceuticals and poly- and perfluoroalkyl substances (PFASs) have been detected in outgoing water from wastewater treatment plants (WWTPs) where the presence of these micropollutants (MPs) has received much attention as these substances have been shown to lead to negative effects on the aquatic environment. The traditional treatment techniques currently used at WWTPs have a limited treatment effect on MPs, where an alternative treatment step for advanced treatment of MPs is required to reduce the emission of these to the environment. This study aimed to investigate the reduction of MPs for the combination of granular activated carbon (GAC) and anion exchange resin (AE) and to investigate which design (i.e., upstream flow with fluidized bed or downstream flow with fixed beds), worked most effectively in terms of operational stability. Furthermore, the work aimed to investigate, based on previously collected data from similar column experiments at Uppsala Water and Waste AB, correlation between total organic carbon (TOC), dissolved organic carbon (DOC) and UVA with pharmaceuticals and PFAS that could be used as a follow-up method in the later full-scale treatment step at Kungsängsverket. The column experiments consisted of seven columns which were divided into three operating lines. Operating line one consisted of a GAC filter with Cyclecarb 401 followed by an AE filter with Purolite 694E, similar design was used for operating line two but with Filtrasorb 400 instead of Cyclecarb 401, both lines with downstream flow. The last operating line consisted of Cyclecarb 401 followed by two AE filters with upstream flow and fluidized beds. Outgoing water from Kungsängsverket WWTP was pumped to each operating line through a pre-treatment consisting of two cartridge filters. In the GAC and AE filters with downstream flow a contact time of 15 and 5 minute respectively, was used, while a contact time of 2 minutes was used for the fluidized AE filters. The reduction efficacy was examined for five selected MPs PFOS, diclofenac, citalopram, metoprolol and oxazepam on two occasions corresponding to 100 and 5 000 treated bed volumes in the GAC filters. Based on the analyzes, the degree of reduction was calculated over the individual filters and over each operating line. Operational stability was examined by comparing the backwashing need for the three operating lines and by examining the reduction of TOC, DOC and UVA over these. The results showed a good reduction of MPs for all operating lines, where the reduction was over 80 percent. Cyclecarb 401 showed a higher reduction of PFOS and diclofenac compared to Filtrasorb 400. Series operation of GAC and AE filters was shown to complement each other, where MPs that showed lower separation in GAC were separated in subsequent AE, which results in a more resource-efficient use of the adsorbents. The stability seen to backwashing needs and reduction was highest for operating line three. The correlation study showed correlation between TOC and UVA with some of the MPs, but more samples would be needed to investigate this further.

Background: Although our knowledge about diatom photosynthesis has made huge progress over the last years, many aspects about their photosynthetic apparatus are still enigmatic. According to published data, the spatial organization as well as the biochemical composition of diatom thylakoid membranes is significantly different from that of higher plants. Results: In this study the pigment protein complexes of the diatom Thalassiosira pseudonana were isolated by anion exchange chromatography. A step gradient was used for the elution process, yielding five well-separated pigment protein fractions which were characterized in detail. The isolation of photosystem (PS) core complex fractions, which contained fucoxanthin chlorophyll proteins (FCPs), enabled the differentiation between different FCP complexes: FCP complexes which were more closely associated with the PSI and PSII core complexes and FCP complexes which built-up the peripheral antenna. Analysis by mass spectrometry showed that the FCP complexes associated with the PSI and PSII core complexes contained various Lhcf proteins, including Lhcf1, Lhcf2, Lhcf4, Lhcf5, Lhcf6, Lhcf8 and Lhcf9 proteins, while the peripheral FCP complexes were exclusively composed of Lhcf8 and Lhcf9. Lhcr proteins, namely Lhcr1, Lhcr3 and Lhcr14, were identified in fractions containing subunits of the PSI core complex. Lhcx1, Lhcx2 and Lhcx5 proteins co-eluted with PSII protein subunits. The first fraction contained an additional Lhcx protein, Lhcx6_1, and was furthermore characterized by high concentrations of photoprotective xanthophyll cycle pigments. Conclusion: The results of the present study corroborate existing data, like the observation of a PSI-specific antenna complex in diatoms composed of Lhcr proteins. They complement other data, like e.g. on the protein composition of the 21 kDa FCP band or the Lhcf composition of FCPa and FCPb complexes. They also provide interesting new information, like the presence of the enzyme diadinoxanthin de-epoxidase in the Lhcx-containing PSII fraction, which might be relevant for the process of non-photochemical quenching. Finally, the high negative charge of the main FCP fraction may play a role in the organization and structure of the native diatom thylakoid membrane. Thus, the results present an important contribution to our understanding of the complex nature of the diatom antenna system.

No description available.

Biocompatibility is an important issue for the development of chromatographic stationary phases for the analysis of biomolecules (including proteins and peptides). A biocompatible stationary phase material is a material that resists nonspecific adsorption of biomolecules and does not interact with them in a way that would alter or destroy their structures or biochemical functions. The monolithic column format is a good alternative to typical spherical particle packed columns for capillary liquid chromatography of biomacromolecules. Several novel anion-exchange polymer monoliths for the analysis of proteins were synthesized for improved biocompatibility. Two novel polymeric monoliths were prepared in a single step by a simple photoinitiated copolymerization of 2-(diethylamino)ethyl methacrylate and polyethylene glycol diacrylate (PEGDA), or copolymerization of 2-(acryloyloxy)ethyl trimethylammonium chloride (AETAC) and PEGDA, in the presence of selected porogens. The resulting monoliths contained functionalities of diethylaminoethyl (DEAE) as a weak anion exchanger and quaternary amine as a strong anion exchanger, respectively. An alternative weak anion exchange monolith with DEAE functionalities was also synthesized by chemical modification after photoinitiated copolymerization of glycidyl methacrylate (GMA) and PEGDA. The dynamic binding capacities of the three monoliths were comparable or superior to values that have been reported for various other monoliths. Chromatographic performances were also similar to those provided by a modified poly(GMA-co-ethylene glycol dimethacrylate) monolith. Separations of standard proteins were achieved under gradient elution conditions using these monolithic columns. This work represents a successful attempt to prepare functionalized monoliths via direct copolymerization of monomers with desired functionalities. Compared to earlier publications, laborious surface modifications were avoided and the PEGDA crosslinker improved the biocompatibility of the monolithic backbone. Protein separations by capillary size exclusion chromatography (SEC) require a monolith that is biocompatible, has sufficient pore volume, has the appropriate pore size distribution, and is rigid. Most polymer monoliths have not possessed a biomodal pore-size distribution, i.e., especially with one distribution in the macropore region and the other in the mesopore region. Furthermore, non-specific adsorption of proteins in these stationary phases has persisted as a major unresolved problem. To overcome these difficulties, a porous poly[polyethylene glycol methyl ether acrylate (PEGMEA)-co-PEGDA] monolith which can resist adsorption of both acidic and basic proteins when using an aqueous buffer without any organic solvent additives was developed. Based on this biocompatible monolith, surfactants were introduced as porogens with the hope of significantly increasing the mesopore volume within the polymer. Two types of surfactants were studied, including poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) or PPO-PEO-PPO and Brij. Pore size distributions were examined using a well-defined molecular weight range series of proteins and peptides by inverse size exclusion chromatography, which indicated relatively large volume percentages of mesopores and micropores. The two new monoliths demonstrated different SEC behaviors, low nonspecific adsorption of proteins, and high mechanical rigidity. High density lipoprotein (HDL) is a heterogeneous class of lipoprotein particles with subspecies that differ in apolipoprotein and lipid composition, size, density, and charge. In this work, I developed a new capillary SEC method for size separation of native HDL particles from plasma using a capillary packed with BioSep-SEC-4000 particles, Three major sizes of HDL particles were separated. Additionally, capillary SEC and capillary strong anion-exchange chromatography of non-delipidated HDL were accomplished using poly(PEGMEA-co-PEGDA) and poly(AETAC-co-PEGDA) monoliths. These new LC methods using packed and monolithic stationary phases provided rapid separation of HDLs and excellent reproducibility.

Oligonucleotides (ONs) are widely used in different applications in life science, forensic, in i.e. family tree DNA test for humans and in diagnostic applications in several fields. The use of ONs in biopharmaceutical therapeutic areas also generates new challenges handling more complex molecules which results in the need of further developed analytical techniques. Anion exchange chromatography (AEX) is a common separation technique for biomolecules and is based on charge attraction between the analyte and the stationary phase. The chromatographic system is complex and often high pH and a high salt concentration is needed for the elution to occur, which in some systems can be corrosive for both the column and the instrument. The aim of this study was to evaluate new mobile phase compositions with lower salt concentrations, organic modifier, and usage of a buffer to increase the control of the pH. This was done by evaluation of three columns developed for AEX and uses different chemical and methodical modification of the mobile phase to control the retention to the stationary phase. The influence of pH, temperature, and methanol (MeOH) content in the buffer were studied by evaluation of resolution, asymmetry, and efficiency responses. Three oligonucleotides with 16, 18 and 19 T-bases in the chain were used in the study of three AIE columns. High pH, elevated temperature and the addition of an organic modifier were used for unfolding of the oligonucleotide chain and generating more efficient separations. Other parameters such as gradient slope and initial concentration of the eluting buffer were also studied, and the findings clearly show that the chromatographic conditions influence the resolution, asymmetry, and efficiency. / Oligonukleotider används i flera olika branscher som forensik och inom life sience till diagnostiska och medicinska applikationer. Eftersom applikationsområdena ökar och forskningen går framåt så blir molekylerna mer komplexa, vilket i sin tur kräver att dom analytiska teknikerna också behöver utvecklas. En vanlig separationsteknik för biomolekyler är anjonbyteskromatografi, då den bygger på laddningsattraktion mellan analyten och den stationära fasen. Oligonukleotider har en negativ nettoladdning på grund av den negativt laddade fosfatgruppen i kedjan. Genom att modifiera de kemiska egenskaperna i den mobila fasen är det därför möjligt att i viss grad kontrollera retentionen till den stationära fasen.       Då det kromatografiska systemet är komplext och det ofta behövs högt pH och/eller en hög saltkoncentration för eluering av analyten kan det i vissa system verka korrosivt för både kolonnen och instrumentet. Det initiala målet med detta arbete var att ta fram olika mobila faser med lägre saltkoncentration, organiskt lösningsmedel och användande av buffer för att kontrollera pH. Detta gjordes genom att utvärdera den kromatografiska kapaciteten hos tre olika anjonbyteskolonner samt använda olika kemiska- och metodiska modifieringar av den mobila fasen för att kontrollera analytens retention. Mer specifikt så kommer påverkan av pH, temperatur och innehåll av metanol i den mobila fasen att studeras genom att utvärdera upplösning, asymmetri och effektivitet i de erhållna kromatogrammen. Analytmixen innehåller tre olika oligonukleotider vilka består av 16, 18 eller 19 T-baser i sekvensen. Genom att höja pH, temperatur och innehåll av metanol i den mobila fasen påvisas mer effektiva separationer. Andra faktorer som gradientlutning och initialkoncentration av den eluerande fasen studeras också med goda resultat när det gäller dess påverkan på upplösning, asymmetri och effektivitet.

The integration of advanced technologies into existing water treatment facilities (WTFs) can improve and enhance water quality; however, these same modifications or improvements may adversely affect finished water provided to the consumer by public water systems (PWSs) that embrace these advanced technologies. Process modification or improvements may unintentionally impact compliance with the provisions of the United States Environmental Protection Agency’s (USEPA’s) Safe Drinking Water Act (SDWA). This is especially true with respect to corrosion control, since minor changes in water quality can affect metal release. Changes in metal release can have a direct impact on a water purveyor’s compliance with the SDWA’s Lead and Copper Rule (LCR). In 2010, the Town of Jupiter (Town) decommissioned its ageing lime softening (LS) plant and integrated a nanofiltration (NF) plant into their WTF. The removal of the LS process subsequently decreased the pH in the existing reverse osmosis (RO) clearwell, leaving only RO permeate and anion exchange (AX) effluent to blend. The Town believed that the RO-AX blend was corrosive in nature and that blending with NF permeate would alleviate their concern. Consequently, a portion of the NF permeate stream was to be split between the existing RO-AX clearwell and a newly constructed NF primary clearwell. The Town requested that the University of Central Florida (UCF) conduct research evaluating how to mitigate negative impacts that may result from changing water quality, should the Town place its AX into ready-reserve. iv The research presented in this document was focused on the evaluation of corrosion control alternatives for the Town, and was segmented into two major components: 1. The first component of the research studied internal corrosion within the existing RO clearwell and appurtenances of the Town’s WTF, should the Town place the AX process on standby. Research related to WTF in-plant corrosion control focused on blending NF and RO permeate, forming a new intermediate blend, and pH-adjusting the resulting mixture to reduce corrosion in the RO clearwell. 2. The second component was implemented with respect to the Town’s potable water distribution system. The distribution system corrosion control research evaluated various phosphate-based corrosion inhibitors to determine their effectiveness in reducing mild steel, lead and copper release in order to maintain the Town’s continual compliance with the LCR. The primary objective of the in-plant corrosion control research was to determine the appropriate ratio of RO to NF permeate and the pH necessary to reduce corrosion in the RO clearwell. In this research, the Langelier saturation index (LSI) was the corrosion index used to evaluate the stability of RO:NF blends. Results indicated that a pH-adjusted blend consisting of 70% RO and 30% NF permeate at 8.8-8.9 pH units would produce an LSI of +0.1, theoretically protecting the RO clearwell from corrosion. The primary objective of the distribution system corrosion control component of the research was to identify a corrosion control inhibitor that would further reduce lead and v copper metal release observed in the Town’s distribution system to below their respective action limits (ALs) as defined in the LCR. Six alternative inhibitors composed of various orthophosphate and polyphosphate (ortho:poly) ratios were evaluated sequentially using a corrosion control test apparatus. The apparatus was designed to house mild steel, lead and copper coupons used for weight loss analysis, as well as mild steel, lead solder and copper electrodes used for linear polarization analysis. One side of the apparatus, referred to as the “control condition,” was fed potable water that did not contain the corrosion inhibitor, while the other side of the corrosion apparatus, termed the “test condition,” was fed potable water that had been dosed with a corrosion inhibitor. Corrosion rate measurements were taken twice per weekday, and water quality was measured twice per week. Inhibitor evaluations were conducted over a span of 55 to 56 days, varying with each inhibitor. Coupons and electrodes were pre-corroded to simulate existing distribution system conditions. Water flow to the apparatus was controlled with an on/off timer to represent variations in the system and homes. Inhibitor comparisons were made based on their effectiveness at reducing lead and copper release after chemical addition. Based on the results obtained from the assessment of corrosion inhibitors for distribution system corrosion control, it appears that Inhibitors 1 and 3 were more successful in reducing lead corrosion rates, and each of these inhibitors reduced copper corrosion rates. Also, it is recommended that consideration be given to use of a redundant single-loop duplicate test apparatus in lieu of a double rack corrosion control test apparatus in experiments where pre-corrosion phases are vi implemented. This recommendation is offered because statistically, the control versus test double loop may not provide relevance in data analysis. The use of the Wilcoxon signed ranks test comparing the initial pre-corroding phase to the inhibitor effectiveness phase has proven to be a more useful analytical method for corrosion studies.

No description available.

Vätgas kan framställas från förnybara energikällor genom vattenelektrolys med anjonbytande membran (AEMWE). AEMWE har vissa fördelar jämfört med traditionell alkalisk vattenelektrolys och elektrolysmed protonledande membran. Till exempel finns det möjlighet att använda alkalisk elektrolyt (även rent vatten) och billiga platinagruppsmetallfria katalysatorer tillsammans med ett anjonbytesmembran. Den största utmaningen med tekniken är att uppnå utmärkt och stabil prestanda för membran och elektroder. AemionTM anjonbytande membran (AEMs) av olika tjocklek, vattenupptag och kapacitet undersöktes i ett AEMWE system med 5 cm2 elektrodarea. Elektrokemisk prestanda hos dessa kommersiella AEM studerades med hjälp av porösa nickel elektroder. Bland de undersökta membranen visade AF2-HWP8-75-X stabil prestanda med en högfrekvent resistans (HFR) på 90 mΩ•cm2 och kunde nå en strömtäthet på 0,8 A/cm2 vid 2,38 V med 1 M KOH vid 60 ˚C.  AEMWE med AF2-HWP8-75-X och olika elektrodkombinationer undersöktes under samma driftsförhållanden. En elektrodkombination med Raney-Ni och NiFeO som katod respektive anod visade bäst prestanda under utvärderingen och gav en strömtäthet på 1,06 och 3,08 A/cm2 vid 2,00 respektive 2,32 V. KOH-lösningens temperatur och koncentration sänktes till 45 ˚C respektive 0,1 M för att undersöka effekten av driftsparametrar på flödescellens prestanda. Flödescellen uppvisade god stabilitet under de nya driftsförhållandena, men dess prestanda minskade avsevärt. Den nådde en strömtäthet på 0,8 A/cm2 vid 2,25 V. / Hydrogen can be produced from renewable energy sources using a novel anion exchange membrane water electrolysis (AEMWE) system. AEMWE has some benefits over the currently used state-of-the-art alkaline and proton exchange membrane water electrolysis systems. For instance, there is a possibility of using alkaline electrolytes (even pure water) and low-cost platinum-group-metal free catalysts together with an ion exchange membrane. However, the main challenge is that the AEMWE system should show excellent and stable performance, depending on the stability of the membrane and the electrodes. AemionTM anion exchange membranes (AEMs) of different thickness and water uptake capacity were investigated using a 5 cm2 AEMWE system. The electrochemical behaviour of these commercial AEMs was studied using nickel (Ni) felt electrodes. Among the investigated AEMs, the AF2-HWP8-75-X showed stable performance with a high frequency resistance (HFR) of 90 mΩ•cm2 and was able to reach a current density of 0.8 A/cm2 at 2.38 V using 1 M KOH at 60 ˚C.  AEMWE systems based on AF2-HWP8-75-X and different electrode combinations were examined under the same operating conditions. An electrode combination with Raney-Ni and NiFeO as cathode and anode, respectively, showed the best performance during the degradation test and provided a current density of 1.06 and 3.08 A/cm2 at 2.00 and 2.32 V, respectively. The operating temperature and concentration of the KOH solution were reduced to 45 ˚C and 0.1 M, respectively, to study the effect of operating parameters on the flow cell performance. The flow cell showed good stability under the new operating conditions, but its performance was reduced significantly. It reached a current density of 0.8 A/cm2 at 2.25 V.