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  • 1. Ahlgren, Joakim
    et al.
    De Brabandere, Heidi
    Reitzel, Kasper
    Rydin, Emil
    Gogoll, Adolf
    Waldeback, Monica
    Sediment phosphorus extractants for phosphorus-31 nuclear magnetic resonance analysis: A quantitative evaluation2007In: Journal of Environmental Quality, ISSN 0047-2425, E-ISSN 1537-2537, Vol. 36, no 3, p. 892-898Article in journal (Refereed)
    Abstract [en]

    The influence of pre-extractant, extractant, and post-extractant on total extracted amounts of P and organic P compound groups measured with 31 P nuclear magnetic resonance (P-31-NMR) in lacustrine sediment was examined. The main extractants investigated were sodium hydroxide (NaOH) and sodium hydroxide ethylenediaminetetraacetic acid (NaOH-EDTA) with bicarbonate buffered dithionite (BD) or EDTA as pre-extractants. Post extractions were conducted using either NaOH or NaOH-EDTA, depending on the main extractant. Results showed that the most efficient combination of extractants for total P yield was NaOH with EDTA as pre-extractant, yielding almost 50% more than the second best procedure. The P compound groups varying the most between the different extraction procedures were polyphosphates and pyrophosphates. NaOH with BD as pre-extractant was the most efficient combination for these compound groups.

  • 2.
    Ahlgren, Ulf
    Umeå University, Faculty of Medicine, Umeå Centre for Molecular Medicine (UCMM).
    Imaging shows insulin-producing cells in diabetes2013In: TrAC. Trends in analytical chemistry, ISSN 0165-9936, E-ISSN 1879-3142, Vol. 44, p. III-IIIArticle in journal (Other (popular science, discussion, etc.))
  • 3.
    Alvarez, Laura
    et al.
    Umeå University, Faculty of Medicine, Molecular Infection Medicine Sweden (MIMS). Umeå University, Faculty of Medicine, Department of Molecular Biology (Faculty of Medicine). Umeå University, Faculty of Medicine, Umeå Centre for Microbial Research (UCMR).
    Hernandez, Sara B
    Umeå University, Faculty of Medicine, Molecular Infection Medicine Sweden (MIMS). Umeå University, Faculty of Medicine, Department of Molecular Biology (Faculty of Medicine). Umeå University, Faculty of Medicine, Umeå Centre for Microbial Research (UCMR).
    de Pedro, Miguel A
    Cava, Felipe
    Umeå University, Faculty of Medicine, Molecular Infection Medicine Sweden (MIMS). Umeå University, Faculty of Medicine, Department of Molecular Biology (Faculty of Medicine). Umeå University, Faculty of Medicine, Umeå Centre for Microbial Research (UCMR).
    Ultra-sensitive, high-resolution liquid chromatography methods for the high-throughput quantitative analysis of bacterial cell wall chemistry and structure2016In: Bacterial cell wall homeostasis: methods and protocols /edited by Hee-Jeon Hong / [ed] Hee-Jeon Hong, New York: Humana Press, 2016, Vol. 1440, p. 11-27Chapter in book (Refereed)
    Abstract [en]

    High-performance liquid chromatography (HPLC) analysis has been critical for determining the structural and chemical complexity of the cell wall. However this method is very time consuming in terms of sample preparation and chromatographic separation. Here we describe (1) optimized methods for peptidoglycan isolation from both Gram-negative and Gram-positive bacteria that dramatically reduce the sample preparation time, and (2) the application of the fast and highly efficient ultra-performance liquid chromatography (UPLC) technology to muropeptide separation and quantification. The advances in both analytical instrumentation and stationary-phase chemistry have allowed for evolved protocols which cut run time from hours (2-3 h) to minutes (10-20 min), and sample demands by at least one order of magnitude. Furthermore, development of methods based on organic solvents permits in-line mass spectrometry (MS) of the UPLC-resolved muropeptides. Application of these technologies to high-throughput analysis will expedite the better understanding of the cell wall biology.

  • 4.
    Andersson, Patrik
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Haglund, Peter
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Tysklind, Mats
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Ultraviolet absorption spectra of all 209 polychlorinated biphenyls evaluated by principal component analysis1997In: Fresenius' Journal of Analytical Chemistry, ISSN 0937-0633, E-ISSN 1432-1130, Vol. 357, no 8, p. 1088-1092Article in journal (Refereed)
    Abstract [en]

    The ultraviolet absorption spectra of all 209 polychlorinated biphenyls (PCBs) were recorded in the range 200-300 nm and displayed two important absorption maxima, viz., the main-band, lambda(max) 200-225 nm, and the kappa-band, lambda(max) 245-265 nm. By utilising principal component analysis, substitution related spectral characteristics of the PCBs, underlying the main patterns of the spectra, were examined. Captured in the multivariate evaluation were e.g., the importance of chlorine atoms in ortho positions, determining the intensity and existence of the kappa-band, chlorine substitution in para-para position, and the total number of chlorine atoms. The measured UV-spectra of all 209 polychlorinated biphenyls provide important physico-chemical descriptors for use in future quantitative structure-activity and structure-property relationship (QSAR/QSPR) studies.

  • 5.
    Appelblad, Patrik
    et al.
    Umeå University, Faculty of Medicine, Department of Clinical Sciences. Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Jonsson, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Bäckström, Torbjörn
    Umeå University, Faculty of Medicine, Department of Clinical Sciences, Obstetrics and Gynaecology.
    Irgum, Knut
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Determination of C-21 ketosteroids in serum using trifluoromethanesulfonic acid catalyzed precolumn dansylation and 1,1’-oxalyldiimidazole postcolumn peroxyoxalate chemiluminescence detection1998In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 70, no 23, p. 5002-5009Article in journal (Refereed)
    Abstract [en]

    A new procedure for the quantitation of C-21 ketosteroids using trifluoromethanesulfonic acid-catalyzed precolumn dansylation and coupled column liquid chromatographic separation, followed by postcolumn 1,1‘-oxalyldiimidazole peroxyoxalate chemiluminescence detection is presented. In the simultaneous optimization of chromatographic resolution and chemiluminescence intensity, a coupled column chromatographic system and a stopped-flow system were used. An eluent containing 20 mM phosphate buffer at pH 6.7 accomplished an efficient separation of 3α-hydroxy-5β-pregnan-20-one from a mixture containing 10 C-21 ketosteroids. Phosphate buffer also proved to be the most advantageous, among the six buffers tested, for sensitive detection. Experimental design and multivariate data analysis were used to characterize and optimize the postcolumn reaction chemistry in the chromatographic system. A valid full factorial design with excellent predictability showed that the flow rates for both 1,1‘-oxalyldiimidazole and hydrogen peroxide were the factors most strongly affecting the sensitivity of the system. The theoretical plate numbers were above 11 000 for all 10 dansylated ketosteroids. The 3σ detection limit estimated from 3α-hydroxy-5β-pregnan-20-one calibration curve data was 1.6 pmol (n = 4, 125 μL injected) and spiked serum containing 0−74 pmol of this compound showed overall recoveries of 73 ± 9% (n = 12). Quantitation of 3α-hydroxy-5β-pregnan-20-one was finally carried out on 45 serum samples and the results compared to those from a radioimmunoassay (RIA) method. The data acquired with the procedure described in this work compare well with the results from RIA, which confirms the reliability of the new analytical procedure.

  • 6. Arshadi, Mehrdad
    et al.
    Nilsson, Calle
    Magnusson, Bengt
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Gas chromatography-mass spectrometry determination of the pentafluorobenzoyl derivative of methylhydrazine in false morel (Gyromitra esculenta) as a monitor for the content of the toxin gyromitrin2006In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1125, no 2, p. 229-233Article in journal (Refereed)
    Abstract [en]

    The main toxic compound found in false morel (Gyromitra esculenta) is acetaldehyde-N-methyl-N-formylhydrazone (gyromitrin). This paper describes a method of determining the total hydrazones content based on acid hydrolysis of gyromitrin and other related hydrazones in air-dried false morel followed by derivatisation of methylhydrazine with pentafluorobenzoyl chloride. The derivative, tris-pentafluorobenzoyl methylhydrazine (tris-PFB-MH) is analyzed by gas chromatography–mass spectrometry. The overall precision of the method is better than 10% (relative standard deviation) for 0.5 ng/μl methylhydrazine in solution. The minimum detectable concentration of methylhydrazine (tris-PFB-MH) by this method is estimated to be approximately 12 pg/μl, which is equal to 0.3 μg/g dry matter (DM) of false morel.

  • 7. Assefa, Anteneh
    et al.
    Tysklind, Mats
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Klanova, Jana
    Wiberg, Karin
    Tracing the sources of PCDD/Fs in Baltic Sea air by using metals as source markers2018In: Environmental Science: Processes & Impacts, ISSN 2050-7887, E-ISSN 2050-7895Article in journal (Refereed)
    Abstract [en]

    The atmosphere is the major contributor of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the Baltic Sea environment. In this study, we investigated the potential of using metals along with PCDD/Fs as markers of important emission sources of PCDD/Fs in air. The air concentrations of PCDD/F congeners (n = 17), other persistent organic pollutants (n = 8) and metals (n = 16) were determined in summer and winter air using high volume samplers at a rural field station (Aspvreten, Sweden) located close to the Baltic Sea coast. During winter, PCDD/F levels were on average 20 times higher than in summer (5.1 +/- 5.8 fg toxicity equivalents (TEQ) m-3 and 0.26 +/- 0.18 fg TEQ m-3, respectively) mostly due to a higher fraction of PCDFs. The increased levels of PCDD/Fs were pronounced mainly in air masses that had travelled from southern (S) and eastern (E) compass sectors. A principal component analysis (PCA) of metal levels in Scots pine (Pinus sylvestris) needles sampled to reflect various air emission source types helped to identify potential marker metals for selected known atmospheric emission sources of PCDD/Fs and to rank among the candidate source types. Brown coal burning, domestic burning and heavy oil burning appeared to be the source types that contribute most of the PCDD/Fs in Baltic Sea air. The current study demonstrates a successful approach for source tracing of PCDD/Fs in air, where integrated indices from seasonal and spatial patterns of PCDD/Fs as well as metal source markers were used to trace and rank sources.

  • 8. Avagyan, Rozanna
    et al.
    Nyström, Robin
    Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics.
    Boman, Christoffer
    Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics.
    Westerholm, Roger
    Determination of hydroxylated polycyclic aromatic hydrocarbons by HPLC-photoionization tandem mass spectrometry in wood smoke particles and soil samples2015In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 407, no 16, p. 4523-4534Article in journal (Refereed)
    Abstract [en]

    A simple and fast method for analysis of hydroxylated polycyclic aromatic hydrocarbons using pressurized liquid extraction and high performance liquid chromatography utilizing photoionization tandem mass spectrometry was developed. Simultaneous separation and determination of nine hydroxylated polycyclic aromatic hydrocarbons and two hydroxy biphenyls could be performed in negative mode with a run time of 12 min, including equilibration in 5 min. The calibration curves were in two concentration ranges; 1-50 ng/mL and 0.01-50 mu g/mL, with coefficients of correlation R (2) > 0.997. The limits of detection and method quantification limits were in the range of 9-56 pg and 5-38 ng/g, respectively. A two-level full factorial experimental design was used for screening of conditions with the highest impact on the extraction. The extraction procedure was automated and suitable for a large number of samples. The extraction recoveries ranged from 70 to 102 % and the matrix effects were between 92 and 104 %. The overall method was demonstrated on wood smoke particles and soil samples with good analytical performance, and five OH-PAHs were determined in the concentration range of 0.19-210 mu g/g. As far as we know, hydroxylated polycyclic aromatic hydrocarbons were determined in wood smoke and soil samples using photoionization mass spectrometry for the first time in this present study. Accordingly, this study shows that high performance liquid chromatography photoionization tandem mass spectrometry can be a good option for the determination of hydroxylated polycyclic aromatic hydrocarbons in complex environmental samples.

  • 9. Axelsson, Sara
    et al.
    Eriksson, Kåre
    Umeå University, Faculty of Medicine, Department of Public Health and Clinical Medicine, Occupational and Environmental Medicine.
    Nilsson, Ulrika
    Determination of resin acids during production of wood pellets-a comparison of HPLC/ESI-MS with the GC/FID MDHS 83/2 method2011In: Journal of Environmental Monitoring, ISSN 1464-0325, E-ISSN 1464-0333, Vol. 13, no 10, p. 2940-2945Article in journal (Refereed)
    Abstract [en]

    Resin acids are constituents of natural and technical products of widespread use. Exposure is known to cause health effects in the airways and on the skin. Liquid chromatography/positive ion electrospray-mass spectrometry (HPLC/pos ESI-MS) was investigated for determination of 7-oxodehydroabietic (7-OXO), dehydroabietic (DHAA) and abietic acid (AA) in wood dust-containing air samples as a derivatisation-free alternative to the GC/FID HSE method 83/2, developed by the Health and Safety Executive UK. The resin acid 7-OXO was measured as a marker for oxidised resin acids, which are known to be the main contact allergens in colophonium. The found detection limits were 0.42 ng m(-3) for 7-OXO, 5.2 ng m(-3) for DHAA and 9.4 ng m(-3) for AA, respectively, which are considerably lower than with the GC/FID method (24, 115 and 89 ng m(-3)). The two methods correlated well, although consistently and significantly lower concentrations of 7-OXO were detected with LC/MS. The higher concentration of this compound with MDHS 83/2 is suggested to be an artefact from the derivatisation step in the presence of soluble wood dust remains.

  • 10.
    Axner, Ove
    et al.
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Galbács, Gábor
    University of Szeged, Szeged, Hungary.
    Laser spectrometric techniques in analytical atomic spectrometry2012In: Encyclopedia of analytical chemistry, John Wiley & Sons, Ltd , 2012Chapter in book (Refereed)
    Abstract [en]

    The main purpose of this article is to describe the theory, instrumentation, and analytical performance of laser analytical atomic spectrometry, focusing on absorption, fluorescence, and ionization techniques. The structure of the article is such that it first provides an outline of the theory of light-matter interactions that prevail for each type of technique as well as of the most common modulation techniques, primarily, wavelength modulation (WM). This is followed by a section that covers the most important types of instrumentation used. The article finally provides a detailed discussion on the specific instrumentation, mode of operation, use, performance, and applications (both analytical and diagnostic) of each technique. In terms of laser atomic absorption, the focus of the discussion is on the use of approaches to enhance the detection capability by either reducing the amount of noise (as is done by the wavelength modulation absorption spectrometry (WMAS) technique) or by providing an extended interaction length (giving rise to cavity-enhanced absorption spectrometry (CEAS) techniques in general, and cavity ring-down spectrometry (CRDS) in particular). Laser atomic fluorescence techniques (often referred to as laser-excited atomic fluorescence spectrometry (LEAFS)) as well as laser ionization techniques (termed either laser-enhanced ionization (LEI) or resonance ionization spectrometry (RIS)) are also covered in some detail. It is shown that several of these techniques are capable of detecting a variety of elements in liquid samples down to low picogram per milliliter (pg mL−1) or parts-per-trillion (ppt) concentrations and in low femtogram amounts. Also other properties of the techniques, e.g. selectivity and linear dynamic range (LDR), are in general superior to those of conventional (nonlaser-based techniques).

  • 11.
    Blum, Kristin
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Targeted and untargeted analysis of organic contaminants from on-site sewage treatment facilities: Removal, fate and environmental impact2018Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    On-site sewage treatment facilities (OSSFs) are widely used all over the world to treat wastewater when large-scale sewage treatment plants (STPs) are not economically feasible. Although there is great awareness that the release of untreated wastewater into the environment can lead to water-related diseases and eutrophication, little is known about organic contaminants and their removal by OSSFs, environmental load and fate. Thus, this PhD thesis aims to improve the knowledge about treatment efficiencies in current OSSFs, the environmental impact and fate of contaminants released from OSSFs, as well as how biochar fortification in sand filter (soil beds) OSSFs might increase removal of these contaminants. State-of-the-art analytical techniques for untargeted and targeted analyses were used and the results evaluated with univariate and multivariate statistics.

    Environmentally-relevant contaminants discharged from OSSFs were identified using untargeted analysis with two-dimensional gas chromatography mass spectrometry (GC×GC-MS) and a MS (NIST) library search in combination with a prioritization strategy based on environmental relevance. A method was successfully developed for the prioritized contaminants using solid phase extraction and GC×GC-MS, and the method was also applicable to untargeted analysis. This method was applied to several studies. The first study compared treatment efficiencies between STP and soil beds and showed that treatment efficiencies are similar or better in soil beds, but the removal among the same type of treatment facilities and contaminants varied considerably. Hydrophilic contaminants were generally inadequately removed in both types of treatment facilities and resulted in effluent levels in the nanogram per liter range.

    Additionally, several prioritized and sometimes badly removed compounds were found to be persistent, mobile, and bioavailable and two additional, untargeted contaminants identified by the NIST library search were potentially mobile. These contaminants were also found far from the main source, a large-scale STP, at Lake Ekoln, which is part of the drinking water reservoir Lake Mälaren, Sweden. The study also showed that two persistent, mobile and bioavailable contaminants were additionally bioaccumulating in perch. Sampling for this study was carried out over several seasons in the catchment of the River Fyris. Parts of this catchment were affected by OSSFs, other parts by STPs. Potential ecotoxicological risks at these sites were similar or higher at those affected by STPs compared to those affected by OSSFs. Mass fluxes per capita were calculated from these levels, which were higher at STP-affected than at OSSF-affected sites in summer and autumn, but not in winter. Possibly, the diffuse OSSF emissions occur at greater average distances from the sampling sites than the STP point emissions, and OSSF-affected sites may consequently be more influenced by fate processes.

    The studies carried out suggested that there is a need to improve current treatment technologies for the removal of hydrophilic contaminants. Thus, the final study of this thesis investigated char-fortified sand filters (soil beds) as potential upgrades for OSSFs using a combination of advanced chemical analysis and quantitative structure-property relationship modeling. Removal efficiencies were calculated from a large variety of contaminants that were identified by untargeted analysis using GC×GC-MS and liquid chromatography ion mobility mass spectrometry as well as library searches (NIST and Agilent libraries). On average, char-fortified sand filters removed contaminants better than sand, partly due to an enhanced removal of several hydrophilic contaminants with heteroatoms. After a two-year runtime, sorption and particularly biodegradation must have contributed to the removal of these compounds.

    Generally, the combination of targeted and untargeted analysis has proven valuable in detecting a large variety of organic contaminants, as well as unexpected ones. The results imply that OSSFs have similar or better removal efficiencies, similar or lower environmental risks and similar or lower mass fluxes per capita, compared to STPs. Biochar fortification can improve the removal of organic contaminants in soil beds, but further research is needed to find technologies that reduce the discharge of all types of organic contaminants.

  • 12.
    Blum, Kristin M.
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Umeå University.
    Gallampois, C.
    Anderson, P. L.
    Renman, G.
    Renman, A.
    Haglund, P.
    Comprehensive assessment of organic contaminant removal from on-site sewage treatment facility effluent by char-fortified filter bedsManuscript (preprint) (Other academic)
    Abstract [en]

    The removal of organic contaminants from wastewater using cost-efficient and easily accessible methods have been increasingly studied in recent years. Most studies have focused on municipal sewage treatment plants; however, our study investigated treatment with char-fortified filter beds for on-site sewage treatment facilities (OSSFs). OSSFs are commonly used in rural and semi-urban areas all over the world to treat wastewater to reduce eutrophication and water-related diseases. To screen for a wide range of organic contaminants in order to improve the understanding of wastewater treatment efficiency and molecular properties, samples were taken from an OSSF field study site that used three filter types: sand, char-fortified sand, and char-fortified gas concrete. First, we screened for organic contaminants with state-of-the-art gas chromatography and liquid chromatography mass spectrometry-based targeted and untargeted analysis and then we developed quantitative structure-property relationship models to find the key molecular features responsible for the removal of organic contaminants. We identified 74 compounds, of which 24 were confirmed with reference standards. Amongst these 74 compounds were plasticizers, UV stabilizers, fragrances, pesticides, surfactant and polymer impurities, pharmaceuticals and their metabolites, and many biogenic compounds. Sand filters that are sometimes used as a last treatment step in OSSFs can remove hydrophobic contaminants. The addition of biochar significantly increases the removal of these and a few hydrophilic compounds (Wilcoxon signed-rank test, α = 0.05). Gas concrete did not appear to be suitable for the removal of organic contaminants. This study showed that, besides hydrophobic effects, biodegradation is the most important removal pathway in long-term field applications. However, further improvements are necessary to remove very hydrophilic contaminants as they were not removed with sand and biochar-fortified sand.

  • 13.
    Blum, Kristin M.
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Umeå University.
    Haglund, P.
    Gao, Q.
    Ahrens, L.
    Gros, M.
    Wiberg, K.
    Anderson, P. L.
    Mass fluxes per capita of organic contaminants from on-site sewage treatment facilitiesManuscript (preprint) (Other academic)
    Abstract [en]

    This study is the first attempt to quantify environmental fluxes per capita of organic contaminants discharged from on-site sewage treatment facilities (OSSFs) in affected recipients. Five sites were monitored around the River Fyris in Sweden: three mainly affected by OSSFs and two mainly affected by municipal sewage treatment plants (STPs). Gas chromatography-mass spectrometry was used to determine environmental concentrations of 30 anthropogenic contaminants, including organophosphorus compounds, rubber and plastic additives, UV stabilizers, fragrances, surfactant ingredients and polycyclic aromatic hydrocarbons. Uni- and multivariate statistical analysis of the most frequently detected contaminants showed that median fluxes per capita of tris(1,3-dichloro-2-propyl) phosphate, tris(1-chloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, and n-butylbenzene sulfonamide were similar at OSSF and STP sites, but the mass fluxes per capita of tris-(2-butoxyethyl) phosphate, 2-(methylthio)benzothiazole, and galaxolide, were significantly lower (~2 to 3-fold) at OSSF sites than at STP sites (Mann-Whitney, α = 0.05). Differences between these sites were larger in samples collected in summer and autumn than in samples collected in winter. Deviations likely originated from differences in treatment technology and distances between source and sampling sites. Further studies are needed to characterize mass fluxes per capita of contaminants in waters that directly receive discharges from OSSFs.

  • 14.
    Bouchet, Sylvain
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Björn, Erik
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Analytical developments for the determination of monomethylmercury complexes with low molecular mass thiols by reverse phase liquid chromatography hyphenated to inductively coupled plasma mass spectrometry2014In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1339, p. 50-58Article in journal (Refereed)
    Abstract [en]

    The behavior of monomethylmercury (MMHg) is markedly influenced by its distribution among complexes with low molecular mass (LMM) thiols but analytical methodologies dedicated to measure such complexes are very scarce up to date. In this work, we selected 15 LMM thiols often encountered in living organisms and/or in the environment and evaluated the separation of the 15 corresponding MMHg-thiol complexes by various high performance liquid chromatography (HPLC) columns. Two C18 (Phenomenex Synergi Hydro-RP and LunaC18(2)), two phenyl (Inertsil Ph 3 and 5 mu m) and one mixed-mode (Restek Ultra IBD) stationary phases were tested for their retention and resolution capacities of the various complexes. The objective was to find simple separation conditions with low organic contents in the mobile phase to provide optimal conditions for detection by inductively coupled plasma mass spectrometry (ICPMS). The 15 complexes were synthesized in solution and characterized by electrospray ionization-mass spectrometry (ESI-MS). The C18 columns tested were either not resolutive enough or too retentive. The 3 pm phenyl stationary phase was able to resolve 10 out of the 15 complexes in less than 25 min, under isocratic conditions. The mixed-mode column was especially effective at separating the most hydrophilic complexes (6 complexes out of the 15), corresponding to the main LMM thiols found in living organisms. The detection limits (DLs) for these two columns were in the low nanomolar range and overall slightly better for the phenyl column. The possibilities offered by such methodology were exemplified by monitoring the time-course concentrations of four MMHg-thiol complexes within a phytoplankton incubation containing MMHg in the presence of an excess of four added thiols. 

  • 15.
    Bruce, Stephen J
    et al.
    Umeå Plant Science Center, Department of Forest Genetics and Plant Physiology, Swedish University of Agricultural Sciences, Umeå, Sweden.
    Jonsson, Pär
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Antti, Henrik
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Cloarec, Olivier
    Technologie Servier, 45000 Orleans, France.
    Trygg, Johan
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Marklund, Stefan L
    Umeå University, Faculty of Medicine, Department of Medical Biosciences, Clinical chemistry.
    Moritz, Thomas
    Umeå Plant Science Center, Department of Forest Genetics and Plant Physiology, Swedish University of Agricultural Sciences, Umeå, Sweden.
    Evaluation of a protocol for metabolic profiling studies on human blood plasma by combined ultra-performance liquid chromatography/mass spectrometry: From extraction to data analysis2009In: Analytical Biochemistry, ISSN 0003-2697, E-ISSN 1096-0309, Vol. 372, no 2, p. 237-249Article in journal (Refereed)
    Abstract [en]

    The investigation presented here describes a protocol designed to perform high-throughput metabolic profiling analysis on human blood plasma by ultra-performance liquid chromatography/mass spectrometry (UPLC/MS). To address whether a previous extraction protocol for gas chromatography (GC)/MS-based metabolic profiling of plasma could be used for UPLC/MS-based analysis, the original protocol was compared with similar methods for extraction of low-molecular-weight compounds from plasma via protein precipitation. Differences between extraction methods could be observed, but the previously published extraction method was considered the best. UPLC columns with three different stationary phases (C8, C18, and phenyl) were used in identical experimental runs consisting of a total of 60 injections of extracted male and female plasma samples. The C8 column was determined to be the best for metabolic profiling analysis on plasma. The acquired UPLC/MS data of extracted male and female plasma samples was subjected to principal component analysis (PCA) and orthogonal projections to latent structures discriminant analysis (OPLS–DA). Furthermore, a strategy for compound identification was applied here, demonstrating the strength of high-mass-accuracy time-of-flight (TOF)/MS analysis in metabolic profiling.

  • 16.
    Bui, Nhat Thi Hong
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Polyhydroxyl and Polyphosphorylcholine functionalized Silica for Hydrophilic interaction liquid Chromatography- Synthesis, characterization and application2012Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    This thesis focuses on the development of new stationary phases for use in hydrophilic interaction liquid chromatography using TRIS-based and phosphorylcholine typed monomers and porous silica particles as starting substrates. In this thesis, several ways of polymerizing highly hydrophilic mono­mers onto pore surfaces of silica supports are described, based on several “grafting from” schemes. “Controlled/living” radical polymerizations including atom transfer radical polymerization (ATRP) and iniferter-mediated polymerization in conjunction with conventional free radical polymerization are demonstrated to be successful tools for grafting different hydrophilic monomers (polyhydroxyl and phosphorylcholine [meth]acrylamide/acrylates) onto the silica surfaces. Reaction solvents are proven to play an essential role to achieve efficient graft polymerization of activated silica surfaces with these amphiphilic vinylic monomers, which is difficult because of their restricted access to the activated surface in solvents that can be used because of solubility constraints.

    Two tentacle TRIS-based polymer grafted silica, namely TRIS-WAX – TRIS functionality bonded to silica via a C–N–C imine bond and TRIS-Amide – TRIS bonded to silica via an amide bond, prove to be useful as stationary phases for hydrophilic interaction chromatography (HILIC).The TRIS-WAX exhibits a mixed mode hydrophilic partitioning and weak anion exchange (HILIC/WAX) retention mechanism while retention by hydrophilic partitioning is the dominant mechanism on the neutral TRIS-Amide phase which lacks weak anion exchange (WAX) properties. Interestingly, both these phases have selectivities that are radically different from most commercial HILIC stationary phases.

    Finally, a method is demonstrated for synthesizing a stratified (graft-copolymerized) silica material based on N,N′-methylenebisacrylamide and 2-methacryloyloxyethyl phosphorylcholine (MPC) using a “controlled/living” photoiniferter-mediated polymerization from the N,N-diethyldithiocarbamate iniferter moiety immobilized silica surfaces. This polymerization method proves to be successful for graft-blockcopolymerization of different highly hydrophilic monomers onto the activated surfaces of porous silica. In this way, silica surfaces are grafted with a cross-linked amide-based hydrogel, on top of which a tentacle zwitterionic phosphorylcholine-typed layer is synthesized. The resulted material proves to be useful for HILIC separations and possesses different selectivity for the tested organic acids compared to that of commercial ZIC-cHILIC stationary phase.

  • 17.
    Byström, Emil
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Porous polymeric materials for chromatography: Synthesis, functionalization and characterization2009Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Background: Separation science is heavily reliant on materials to fulfill ever more complicated demands raised by other areas of science, notably the rapidly expanding molecular biosciences and environmental monitoring. The key to successful separations lies in a combination of physical properties and surface chemistry of stationary phases used in liquid chromatographic separation, and this thesis address both aspects of novel separation materials.

    Methods: The thesis accounts for several approaches taken during the course of my graduate studies, and the main approaches have been i) to test a wild-grown variety of published methods for surface treatment of fused silica capillaries, to ascertain firm attachment of polymeric monoliths to the wall of microcolumns prepared in silica conduits; ii) developing a novel porogen scheme for organic monoliths including polymeric porogens and macromonomers; iii) evaluating a mesoporous styrenic monolith for characterization of telomers intended for use in surface modification schemes and; iv) to critically assess the validity of a common shortcut used for estimating the porosity of monoliths prepared in microconduits; and finally v) employing plasma chemistry for activating and subsequently modifying the surface of rigid, monodisperse particles prepared from divinylbenzene.

    Results: The efforts accounted for above have resulted in i) better knowledge of the etching and functionalization parameters that determine attachment of organic monoliths prepared by radical polymerization to the surface of silica; ii) polar methacrylic monoliths with a designed macroporosity that approaches the desired "connected rod" macropore morphology; iii) estab¬lishing the usefulness of monoliths prepared via nitroxide mediated polymerization in gradient polymer elution chromatography; iv) proving that scanning electron microscopy images are of limited value for assessing the macroporous properties of organic monoliths, and that pore measurements on externally polymerized monolith cocktails do not represent the porous properties of the same cocktail polymerized in narrow confinements; and v) showing that plasma bromination can be used as an activation step for rigid divinylbenzene particles to act as grafting handles for epoxy-containing telomers, that can be attached in a sufficiently dense layer and converted into carboxylate cation exchange layer that allows protein separations in fully aqueous eluents.

  • 18.
    Byström, Emil
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Viklund, Camilla
    Merck SeQuant AB, Umeå.
    Irgum, Knut
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Differences in porous characteristics of styrenic monoliths prepared by controlled thermal polymerization in molds of varying dimensions2010In: Journal of Separation Science, ISSN 1615-9306, E-ISSN 1615-9314, Vol. 33, no 2, p. 191-199Article in journal (Refereed)
    Abstract [en]

    Nitroxide-mediated polymerization was used as a model system for preparing styrenic monolithic materials with significant mesopore contents in different mold formats, with the aim of assessing the validity of pore characterization of capillary monoliths by analysis of parallel bulk polymerized precursor solution. Capillary monoliths were prepared in 250 mm id fused silica tubes (quadruplicate samples, in total 17 m), and the batch polymerizations were carried out in parallel in 100 mL microvials and regular 2mL glass vials, both in quintuplicate. The monoliths recovered from the molds were characterized for their meso- and macroporous properties by nitrogen sorptiometry (three repeated runs on each sample), followed by a single analysis by mercury intrusion porosimetry. A total of 14 monolith samples were thus analyzed. A Grubbs’ test identified one regular vial sample as an outlier in the sorptiometric surface area measurements, and data from this sample were consequently excluded from the pore size calculations, which are based on the same nitrogen sorption data, and also from the mercury intrusion data set. The remaining data were subjected to single factor analyses of variance analyses to test if the porous properties of the capillary monoliths were different from those of the bulk monoliths prepared in parallel. Significant differences were found between all three formats both in their meso and macroporous properties. When the dimension was shrunk from conventional vial to capillary size, the specific surface area decreased from 52.274.7 to 34.671.7m2/g. This decrease in specific surface area was accompanied by a significant shift in median diameter of the through-pores, from 31073.9 to 544713 nm. None of these differences was obvious from the scanning electron micrographs that were acquired for each sample type. The common practice of determining the mesopore characteristics from analysis of samples prepared by parallel bulk polymerization and looking for changes in the macropore structure by visual assessment of SEMs are therefore both rather questionable, at least for monoliths of the kind used in this study.

  • 19.
    Carlsson, Sofia
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Installation of a hydride generation system coupled to atomic absorption spectrometry in Vientiene, Laos PDR - Determination of arsenic in water samples 2012Independent thesis Advanced level (degree of Master (One Year)), 20 credits / 30 HE creditsStudent thesis
    Abstract [en]

    Until now, the possibility for the personnel at the National University of Lao PDR (NUOL) to perform analysis of arsenic in drinking water as well as water used for agriculture has been limited to indication sticks, giving only a vague indication of the presence and levels of arsenic. Due to the lack of adequate and sensitive analytical instruments the levels of arsenic are relatively unknown in Lao People Democratic Republic (Lao PDR). A simple method of analyzing arsenic in water is using atomic absorption spectroscopy (AAS) coupled to a hydride generation system (HG). In support of this project, an HG with an AAS-oven has been delivered and installed at the inorganic lab at NUOL. The system has been optimized and tested and the personnel at the university have been instructed and trained in how to use the system. Sampling and analysis were supposed to be executed although this part of the project encountered many problems and could not be performed in a satisfactory way. Problems mainly came from lack of material, i.e. distilled water, and knowledge as well as monsoon weather conditions making the sampling impossible.

  • 20.
    Cedergren, Anders
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Nordmark, Ulrika
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Determination of water in NIST reference material for mineral oils2000In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 72, no 14, p. 3392-3395Article in journal (Refereed)
    Abstract [en]

    The accuracy of the reference concentrations of moisture in electrical insulating oil RM 8506 and lubricating oil RM 8507 (both of mineral type) and specified by the National institute of Standards and Technology (NIST) as containing 39.7 and 76.8 ppm (w/w) water, respectively, has recently been the subject of debate in this journal. To shed some further light on this controversy, we report in this correspondence results for these oils obtained by two additional methods, one based on specially designed reagents for diaphragm-free Karl Fischer (KF) coulometry and the other based on the concept of stripping at elevated temperature/continuous KF coulometry. A positive interference effect was shown to take place for RM 8506 when the direct coulometric method was used. If the results are corrected for this, the values including six different procedures varied in the range 13.5-15.6 ppm (w/w). For RM 8507, all values were between 42.5 and 47.2 ppm (w/w), which means that the values recommended by NIST for both reference oils using volumetric titration are about twice as high as those obtained with the other techniques. A possible explanation for this discrepancy is presented.

  • 21. Chaintreau, Alain
    et al.
    Fieber, Wolfgang
    Sommer, Horst
    Gilbert, Alexis
    Yamada, Keita
    Yoshida, Naohiro
    Pagelot, Alain
    Moskau, Detlef
    Moreno, Aitor
    Schleucher, Jürgen
    Umeå University, Faculty of Medicine, Department of Medical Biochemistry and Biophysics.
    Reniero, Fabiano
    Holland, Margaret
    Guillou, Claude
    Silvestre, Virginie
    Akoka, Serge
    Remaud, Gerald S
    Site-specific C-13 content by quantitative isotopic C-13 nuclear magnetic resonance spectrometry: a pilot inter-laboratory study2013In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 788, p. 108-113Article in journal (Refereed)
    Abstract [en]

    Isotopic C-13 NMR spectrometry, which is able to measure intra-molecular C-13 composition, is of emerging demand because of the new information provided by the C-13 site-specific content of a given molecule. A systematic evaluation of instrumental behaviour is of importance to envisage isotopic C-13 NMR as a routine tool. This paper describes the first collaborative study of intra-molecular C-13 composition by NMR. The main goals of the ring test were to establish intra-and inter-variability of the spectrometer response. Eight instruments with different configuration were retained for the exercise on the basis of a qualification test. Reproducibility at the natural abundance of isotopic C-13 NMR was then assessed on vanillin from three different origins associated with specific delta C-13(i) profiles. The standard deviation was, on average, between 0.9 and 1.2 parts per thousand for intra-variability. The highest standard deviation for inter-variability was 2.1%. This is significantly higher than the internal precision but could be considered good in respect of a first ring test on a new analytical method. The standard deviation of delta C-13(i) in vanillin was not homogeneous over the eight carbons, with no trend either for the carbon position or for the configuration of the spectrometer. However, since the repeatability for each instrument was satisfactory, correction factors for each carbon in vanillin could be calculated to harmonize the results.

    (C) 2013 Elsevier B.V. All rights reserved.

  • 22.
    Chen, Yang-Er
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry. College of Life Sciences, Sichuan Agricultural University, Ya'an, China.
    Yuan, Shu
    Schröder, Wolfgang P.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Comparison of methods for extracting thylakoid membranes of Arabidopsis plants2016In: Physiologia Plantarum: An International Journal for Plant Biology, ISSN 0031-9317, E-ISSN 1399-3054, Vol. 156, no 1, p. 3-12Article in journal (Refereed)
    Abstract [en]

    Robust and reproducible methods for extracting thylakoid membranes are required for the analysis of photosynthetic processes in higher plants such as Arabidopsis. Here, we compare three methods for thylakoid extraction using two different buffers. Method I involves homogenizing the plant material witha metal/glass blender; method II involves manually grinding the plant materialin ice-cold grinding buffer with a mortar and method III entails snap-freezing followed by manual grinding with a mortar, after which the frozen powder is thawed in isolation buffer. Thylakoid membrane samples extracted using each method were analyzed with respect to protein and chlorophyll content, yields relative to starting material, oxygen-evolving activity, protein complex content and phosphorylation. We also examined how the use of fresh and frozen thylakoid material affected the extracts’ contents of protein complexes. The use of different extraction buffers did not significantly alter the protein contentof the extracts in any case. Method I yielded thylakoid membranes with the highest purity and oxygen-evolving activity. Method III used low amounts of starting material and was capable of capturing rapid phosphorylation changes in the sample at the cost of higher levels of contamination. Method II yielded thylakoid membrane extracts with properties intermediate between those obtained with the other two methods. Finally, frozen and freshly isolated thylakoid membranes performed identically in blue native-polyacrylamide gel electrophoresis experiments conducted in order to separate multimeric protein supracomplexes.

  • 23.
    Courtois, Julien
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Monolithic separation media synthesized in capillaries and their applications for molecularly imprinted networks2006Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    The thesis describes the synthesis of chromatographic media using several different approaches, their characterizations and applications in liquid chromatography. The steps to achieve a separation column for a specific analyte are presented. The main focus of the study was the design of novel molecularly imprinted polymers.

    Attachment of monolithic polymeric substrates to the walls of fused silica capillaries was studied in Paper I. With a broad literature survey, a set of common methods were tested by four techniques and ranked by their ability to improve anchoring of polymers. The best procedure was thus used for all further studies.

    Synthesis of monoliths in capillary columns was studied in Paper II. With the goal of separating proteins without denaturation, various monoliths were polymerized in situ using a set of common monomers and cross-linkers mixed with poly(ethylene glycol) as porogen. The resulting network was expected to present “protein-friendly pores”. Chemometrics were used to find and describe a set of co-porogens added to the polymerization cocktails in order to get good porosity and flow-through properties.

    Assessment of the macroporous structure of a monolith was described in Paper III. An alternative method to mercury intrusion porosimetry was proposed. The capillaries were embedded in a stained resin and observed under transmission electron microscope. Images were then computed to determine the pore sizes.

    Synthesis of molecularly imprinted polymers grafted to a core mono-lith in a capillary was described in Paper IV. The resulting material, imprinted with local anaesthetics, was tested for its chromatographic performance. Similar imprinted polymers were characterized by microcalorimetry in Paper V. Finally, imprinted monoliths were also synthesized in a glass tube and further introduced in a NMR rotor to describe the interactions between stationary phase and template in Paper VI.

  • 24. De Brabandere, Heidi
    et al.
    Danielsson, Rolf
    Sjoberg, Per J. R.
    Ahlgren, Joakim
    Rydin, Emil
    Waldeback, Monica
    Sediment extraction and clean-up for organic phosphorus analysis by electrospray ionization tandem mass spectrometry2008In: Talanta: The International Journal of Pure and Applied Analytical Chemistry, ISSN 0039-9140, E-ISSN 1873-3573, Vol. 74, no 5, p. 1175-1183Article in journal (Refereed)
    Abstract [en]

    A method to prepare NaOH sediment extracts for organic P compound analysis with electrospray ionization tandem mass spectrometry (ESI-MS-MS) was developed on natural samples. Ion exchange, rotary evaporation and mass cut-off filtering proved to be suitable for sample preparation. Samples were analyzed with ESI-MS-MS, and reproducibility and repeatability of the method was calculated. In addition, P-31-nuclear magnetic resonance Spectroscopy (P-31 NMR)was used to measure recovery of different P compound groups such as orthophosphate (Ortho-P), orthophosphate monoesters (Monoester-P), orthophosphate diesters (Diester-P) and pyrophosphates (Pyro-P). The developed sample preparation method resulted in an easy-to-spray liquid for the ESI-MS-MS instrumentation. The overall P recovery was 65% and P-31 NMR showed that Diester-P, possibly in the form of DNA, was apparently lost through the filtering step most likely due to their size. Variances in the total intensities of the MS scans (relative standard deviation (R.S.D.) 35-54%) were for about 50% due to repeated MS runs. Covariances of the peaks in the MS spectra were calculated to be for about 30% due to the sample preparation procedure. Finally, with the ESI-MS-MS approach, 11 peaks in the mass spectra were found likely to represent phosphate containing compounds. (c) 2007 Elsevier B.V. All rights reserved.

  • 25.
    Dinh, Ngoc Phuoc
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Investigations of the retention mechanisms in hydrophilic interaction chromatography2013Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Hydrophilic interaction chromatography is well known as a powerful technique separation of polar and ionizable compound nowadays. However the retention mechanism of the technique is still under debate. Understanding retention mechanism would facilitate the method development using the technique and its future improvement. This was inspiring and became the goal of this thesis.

    This work involves the characterization of the water enriched layer regarding to water and buffer salt accumulation. Twelve HILIC stationary phase with a diverse surface chemistry regarding to function groups and modification type were studied. Effect of water and salt on regarding to the retention mechanism was investigated by correlating the adsorption data to the retention of selected solutes

    This also involved the characterization of interactions involve in the separation of 21 HILIC columns. Interactions was probe by retention ratio of pair solutes which are characteristic for each specific interaction. The data was evaluate using principle component analysis – a multivariable data analysis method. The model was comprehensive and its outcomes were confirmed by the studies on adsorptions of water and salts.

  • 26.
    Dinh, Ngoc Phuoc
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Jonsson, Tobias
    Merck SeQuant AB, S-90719 Umeå, Sweden.
    Irgum, Knut
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Accumlations of ammonium acetate on polar materials under HILIC condition and its relation to retention of analytesManuscript (preprint) (Other academic)
    Abstract [en]

    Ammonium acetate is a buffer salt commonly added to mobile phase in HILIC to improve the reproducibility of the retention of analytes. Adding buffer salt would then result to the change in retention and selectivity. In this study, we have developed methods for determine ammonium acetate in form of its hydrolyzed products (ammonium ion and acetate ion) adsorption on twelve different HILIC stationary phases under various mobile phase condition. The effect of functional group and mobile phase compositions on salt adsorption was then discussed. We also tried to develop a method for characterization important retention mechanism of HILIC systems and interpreted them under the relationship with salt adsorption. Adsorption of salt was based on both portioning and electrostatic interaction. Ammonium was found to preferentially adsorb on HILIC stationary phases except Purospher Star NH2 phase. It is worth noting that adding salt to mobile phase can promote partitioning retention mechanism, possibly as a result of phase separation due to salt out effect.

  • 27.
    Dinh, Ngoc Phuoc
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Merck SeQuant AB, Umeå.
    Jonsson, Tobias
    Merck SeQuant AB, Umeå.
    Irgum, Knut
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Water uptake on polar stationary phases under conditions for hydrophilic interaction chromatography and its relation to solute retention2013In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1320, p. 33-47Article in journal (Other academic)
    Abstract [en]

    In hydrophilic interaction chromatography, water is known to accumulate on the stationary phase to form a water enriched layer, which is believed to play an important role in the retention mechanism. To gain a better understanding retention mechanism in HILIC, we have determined the water uptake on twelve different HILIC stationary phases. Non-modified and monomerically functionalized silica phases followed a pattern of monolayer formation followed by multiple layer adsorption, while the water uptake on polymerically functionalized silica stationary phase showed the characteristics of formation and swelling of hydrogels. This difference in the nature of water accumulation was found to be related to different water uptake patterns when methanol and tetrahydrofuran were added to 80:20 % (v/v) acetonitrile/water by replacing 5 % of the acetonitrile as tertiary solvents, and also when ammonium acetate was added as buffering electrolyte. The relationship between water uptake and retention mechanism was investigated by looking at the correlation between retention factors of neutral analytes and phase ratios of HILIC columns, calculated either as surface area (adsorption) or volume of the water layer enriched from the acetonitrile/water eluent (partitioning). Regardless of the adsorption or partitioning mechanism, the interaction of neutral analytes and stationary phase could be mainly the hydrogen bonding between analytes and the accumulated water in the water enriched layer.

  • 28.
    Dinh, Ngoc Phuoc
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Nguyen, Anh Mai
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Quach, Minh Cam
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Shchukarev, Andrei
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Irgum, Knut
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Functionalization of epoxy-based monoliths for ion exchange chromatography of proteins2009In: Journal of Separation Science, Vol. 32, no 15-16, p. 2556-2564Article in journal (Refereed)
    Abstract [en]

    Macroporous epoxy-based monoliths prepared by emulsion polymerization have been modified for use in ion exchange chromatography (IEC) of proteins. Strong anion exchange functionality was established by iodomethane quaternization of tertiary amine present on the monolith surface as a part of the polymer backbone. The modification pathway to cation exchange materials was via incorporation of glycidyl methacrylate (GMA) brushes which were coated using atom transfer radical polymerization (ATRP). Strong (SO3-) and weak (COO-) cation exchange groups were thereafter introduced onto the GMA-grafted monoliths by reactions with sodium hydrogen sulfite and iminodiacetic acid, respectively. Grafting was confirmed by XPS, gravimetric measurement, and chromatographic behavior of the modified materials toward model proteins. In incubation experiments the proteins were recovered quantitatively with no obvious signs of unfolding after contact with the stationary phase for >2 h. Chromatographic assessments on the functionalized columns as well as problems associated with flow-through modification by ATRP are discussed.

  • 29.
    Do, Lan
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    New tools for sample preparation and instrumental analysis of dioxins in environmental samples2013Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), two groups of structurally related chlorinated aromatic hydrocarbons, are of high concern due to their global distribution and extreme toxicity. Since they occur at very low levels, their analysis is complex, challenging and hence there is a need for efficient, reliable and rapid alternative analytical methods. Developing such methods was the aim of the project this thesis is based upon.

    During the first years of the project the focus was on the first parts of the analytical chain (extraction and clean-up). A selective pressurized liquid extraction (SPLE) procedure was developed, involving in-cell clean-up to remove bulk co-extracted matrix components from sample extracts. It was further streamlined by employing a modular pressurized liquid extraction (M-PLE) system, which simultaneously extracts, cleans up and isolates planar PCDD/Fs in a single step. Both methods were validated using a wide range of soil, sediment and sludge reference materials. Using dichloromethane/n-heptane (DCM/Hp; 1/1, v/v) as a solvent, results statistically equivalent to or higher than the reference values were obtained, while an alternative, less harmful non-chlorinated solvent mixture - diethyl ether/n-heptane (DEE/Hp; 1/2, v/v) – yielded data equivalent to those values.

    Later, the focus of the work shifted to the final instrumental analysis. Six gas chromatography (GC) phases were evaluated with respect to their chromatographic separation of not just the 17 most toxic congeners (2,3,7,8-substituted PCDD/Fs), but all 136 tetra- to octaCDD/Fs. Three novel ionic liquid columns performed much better than previously tested commercially available columns. Supelco SLB-IL61 offered the best overall performance, successfully resolving 106 out of the 136 compounds, and 16 out of the 17 2,3,7,8-substituted PCDD/Fs. Another ionic liquid (SLB-IL111) column provided complementary separation. Together, the two columns separated 128 congeners. The work also included characterization of 22 GC columns’ selectivity and solute-stationary phase interactions. The selectivities were mapped using Principal Component Analysis (PCA) of all 136 PCDD/F’s retention times on the columns, while the interactions were probed by analyzing both the retention times and the substances’ physicochemical properties.

  • 30.
    Do, Lan
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Lundstedt, Staffan
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Haglund, Peter
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Optimization of selective pressurized liquid extraction for extraction and in-cell clean-up of PCDD/Fs in soils and sediments2013In: Chemosphere, ISSN 0045-6535, E-ISSN 1879-1298, Vol. 90, no 9, p. 2414-2419Article in journal (Refereed)
    Abstract [en]

    This paper describes the development of methods for selective extraction of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from soils and sediments, using pressurized liquid extraction with in-cell clean-up (SPLE). Two binary solvent mixtures, viz. dichloromethane/n-heptane (DCM/Hp), and diethylether/n-heptane (DEE/Hp), were evaluated. The SPLE extraction conditions were optimized using central composite face (CCF) design. Three factors were investigated: extraction temperature (60-160°C), number of extraction cycles (1-3) and time per cycle (2-18min). The results showed that DCM/Hp (1/1, v/v) and DEE/Hp (1/2, v/v) were the best extraction solvent compositions and that the extraction temperature was a critical factor that needed careful optimization to achieve high extraction efficiency without co-extraction of sulfuric acid. Under the optimal conditions, the SPLE methods provided results with good accuracy and precision. For the sandy soil certified reference material (CRM-529) the quantification results ended up in the range 82-110% as compared to the concentrations obtained by a reference method based on Soxhlet extraction and external column clean-up. Furthermore, for a clay soil (CRM-530) and a sediment reference material (WMS-01), the accuracy (trueness) of the TEQ values were +11% (DCM/Hp) and +8% (DEE/Hp) for CRM-530, +8% and -7% for WMS-01, respectively. The individual congener concentrations also agreed well with the certified values. These findings show that SPLE is a promising method for combined extraction and clean-up of PCDD/Fs in soil/sediment samples.

  • 31.
    Do, Lan
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Xuan, Thong H.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Lundstedt, Staffan
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Haglund, Peter
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Modular pressurized liquid extraction for simultaneous extraction, clean-up and fractionation of PCDD/Fs in soil, sediment and sludge samples2013In: Analytical Methods, ISSN 1759-9660, E-ISSN 1759-9679, no 5, p. 1231-1237Article in journal (Refereed)
    Abstract [en]

    Modular pressurized liquid extraction (M-PLE) procedures were developed for simultaneous extraction, clean-up and fractionation of polychlorinated dioxins and furans (PCDD/Fs) in soil, sediment and sludge samples. The procedures utilize two coupled extraction cells: an upstream cell filled with the sample and layers of silica and acid- and base-modified silica, and a downstream cell filled with activated carbon. The silica layers were added to remove polar or hydrolysable matrix components, and the carbon to perform planarity-based fractionation. Two solvent systems (dichloromethane–heptane, DCM–Hp and diethyl ether–heptane, DEE–Hp) and two activated carbon loads (1% and 3% carbon on Celite) were evaluated using certified reference materials (CRM-529 and WMS-01) and materials from previous inter-calibration studies. Using any of the four procedures, data statistically equivalent to the certified or reference values were obtained. The M-PLE procedure using DCM–Hp and 1% carbon sometimes extracted the reference materials more efficiently than the reference methods, while the DEE–Hp procedure extracted them equally efficient, offering an alternative with less environmental impact. The methods with 1% carbon on Celite produced sufficiently pure extracts for sample loads up to one gram, but for greater sample loads the higher carbon load (3% carbon on Celite) was required to avoid breakthrough of target analytes. The new streamlined procedures are fast, cost-efficient, involve relatively low environmental impact (in the case of DEE–Hp) and are well suited for high-throughput analysis of solid samples, e.g. in connection with environmental monitoring campaigns and major soil remediation efforts.

  • 32.
    Elhaj, Ahmed
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Porous Polymeric Monoliths by Less Common Pathways: Preparation and Characterization2014Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    This thesis focuses on my endeavors to prepare new porous polymeric monoliths that are viable to use as supports in flow-through processes. Polymer monoliths of various porous properties and different chemical properties have been prepared utilizing the thermally induced phase separation (TIPS) phenomenon and step-growth polymerization reactions. The aim has been to find appropriate synthesis routes to produce separation supports with fully controlled chemical, physical and surface properties. This thesis includes preparation of porous monolithic materials from several non-cross-linked commodity polymers and engineering plastics by dissolution/precipitation process (i.e. TIPS). Elevated temperatures, above the upper critical solution temperature (UCST), were used to dissolve the polymers in appropriate solvents that only dissolve the polymers above this critical temperature. After dissolution, the homogeneous and clear polymer-solvent solution is thermally quenched by cooling. A porous material, of three dimensional structure, is then obtained as the temperature crosses the UCST. More than 20 organic solvents were tested to find the most compatible one that can dissolve the polymer above the UCST and precipitate it back when the temperature is lowered. The effect of using a mixture of two solvents or additives (co-porogenic polymer or surfactant) in the polymer dissolution/precipitation process have been studied more in depth for poly(vinylidine difluoride) (PVDF) polymers of two different molecular weight grades. Monolithic materials showing different pore characteristics could be obtained by varying the composition of the PVDF-solvent mixture during the dissolute­ion/precipitation process. Step-growth polymerization (often called polycondensat­ion reaction) combined with sol-gel process with the aid of porogenic polymer and block copolymer surfactant have also been used as a new route of synthesis for production of porous melamine-formaldehyde (MF) monoliths. In general, the meso- and macro-porous support materials, for which the synthesis/preparation is discussed in this thesis, are useful to a wide variety of applications in separation science and heterogeneous reactions (catalysis).

  • 33. Eriksson, Lennart
    et al.
    Trygg, Johan
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Wold, Svante
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Umetrics Inc., 42 Pine Hill Rd, Hollis, NH 03049, USA.
    PLS-trees (R), a top-down clustering approach2009In: Journal of Chemometrics, ISSN 0886-9383, E-ISSN 1099-128X, Vol. 23, no 11, p. 569-580Article in journal (Refereed)
    Abstract [en]

    A hierarchical clustering approach based on a set of PLS models is presented. Called PLS-Trees (R), this approach is analogous to classification and regression trees (CART), but uses the scores of PLS regression models as the basis for splitting the clusters, instead of the individual X-variables. The split of one cluster into two is made along the sorted first X-score (t(1)) of a PLS model of the cluster, but may potentially be made along a direction corresponding to a combination of scores. The position of the split is selected according to the improvement of a weighted combination of (a) the variance of the X-score, (b) the variance of Y and (c) a penalty function discouraging an unbalanced split with very different numbers of observations. Cross-validation is used to terminate the branches of the tree, and to determine the number of components of each cluster PLS model. Some obvious extensions of the approach to OPLS-Trees and trees based on hierarchical PLS or OPLS models with the variables divided in blocks depending on their type, are also mentioned. The possibility to greatly reduce the number of variables in each PLS model on the basis of their PLS w-coefficients is also pointed out. The approach is illustrated by means of three examples. The first two examples are quantitative structure-activity relationship (QSAR) data sets, while the third is based on hyperspectral images of liver tissue for identifying different sources of variability in the liver samples.

  • 34. Evertsson, Emma
    et al.
    Rönnberg, Julia
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Stalring, Jonna
    Thunberg, Linda
    A hierarchical screening approach to enantiomeric separation2017In: Chirality, ISSN 0899-0042, E-ISSN 1520-636X, Vol. 29, no 5, p. 202-212Article in journal (Refereed)
    Abstract [en]

    The screening of a number of chiral stationary phases (CSPs) with different modifiers in supercritical fluid chromatography to find a chromatographic method for separation of enantiomers can be time-consuming. Computational methods for data analysis were utilized to establish a hierarchical screening strategy, using a dataset of 110 drug-like chiral compounds with diverse structures tested on 15 CSPs with two different modifiers. This dataset was analyzed using a combinatorial algorithm, principal component analysis (PCA), and a correlation matrix. The primary goal was to find a set of eight columns resolving a large number of compounds, but also having complementary enantioselective properties. In addition to the hereby defined hierarchical experimental strategy, quantitative structure enantioselective models (QSERs) were evaluated. The diverse chemical space and relatively limited size of the training set reduced the accuracy of the QSERs. However, including separation factors from other CSPs increased the accuracies of the QSERs substantially. Hence, such combined models can support the experimental strategy in prioritizing the CSPs of the second screening phase, when a compound is not separated by the primary set of columns.

  • 35. Fick, J.
    et al.
    Pommer, L.
    Andersson, B.
    Nilsson, C.
    Experimental design as a tool to study gas-phase reactions in ventilation ducts2002Conference paper (Refereed)
  • 36.
    Galindo-Prieto, Beatriz
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Eriksson, Lennart
    MKS Umetrics, Umeå, Sweden.
    Trygg, Johan
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Variable influence on projection (VIP) for orthogonal projections to latent structures (OPLS)2014In: Journal of Chemometrics, ISSN 0886-9383, E-ISSN 1099-128X, Vol. 28, no 8, p. 623-632Article in journal (Refereed)
    Abstract [en]

    A new approach for variable influence on projection (VIP) is described, which takes full advantage of the orthogonal projections to latent structures (OPLS) model formalism for enhanced model interpretability. This means that it will include not only the predictive components in OPLS but also the orthogonal components. Four variants of variable influence on projection (VIP) adapted to OPLS have been developed, tested and compared using three different data sets, one synthetic with known properties and two real-world cases.

  • 37.
    Goitom Asfaha, Daniel
    Umeå University, Faculty of Science and Technology, Chemistry.
    Fundamental Studies on Direct Injection Nebulisers for Sample Introduction in ICP Spectrometry: Aerosol Properties, ICP Characteristics and Analytical Performance2006Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    The performance of different types of nebulisers: Vulkan direct injection nebuliser (Vulkan DIN), direct injection high efficiency nebuliser (DIHEN), microconcentric nebuliser coupled to cyclonic or double pass spray chamber (MCN-C or MCN-DP, respectively) was investigated and compared when used for sample introduction to ICP-MS or ICP-OES. With ICP-OES, in axial viewing mode, intensity distributions across the radius of the plasma (radial intensity profiles) were determined for different spectral lines with Esum 1.85-15.41 eV to determine fundamental plasma properties for various matrices using Vulkan DIN and MCN-C. The results showed that with the MCN-C the ionisation temperature (Tion) was about the same across the measured region of the plasma (±3.0 mm) whereas with the Vulkan DIN the Tion was significantly lower in the centre of the plasma. A large deviation from local thermodynamic equilibrium, as well as deteriorated stability, was observed for the plasma when using the Vulkan DIN.

    With ICP-MS noise power spectra (NPS) were generated to identify sources of noise. NPS showed that the magnitude of white noise for the tested sample introduction systems decreased in the following order: Vulkan DIN > DIHEN > MCN-C > MCN-DP. This order follows the decrease of mean droplet size and span of the size distribution, indicating that the white noise is caused by spatial and temporal non-uniform desolvation and ionisation. Another source of noise arose from the peristaltic pump and the magnitude of pump interference noise decreased in the following order: DIHEN > MCN-C/DP > Vulkan DIN. Mains power interference noise and 1/f noise were lower for the direct injection nebulisers compared to the spray chamber systems. The contribution or effects of these noise components on relative standard deviations of steady-state ion-count rate and isotope ratio measurements is discussed in this thesis.

    Aerosols generated by the Vulkan DIN and the DIHEN were also directly characterised using Particle Dynamic Analysis. The Vulkan DIN produced particles with a mean diameter of ~30 µm and a size distribution between 2-80 µm. With the DIHEN the corresponding values were ~11 µm and 1-40 µm, respectively, with a few particles at 55-78 µm. The mean velocity of particles from the Vulkan DIN was ~10 m s-1 and from the DIHEN ~18 m s-1. The lower velocity allows longer residence time counteracting the effects of the larger droplet size.

  • 38. Grabicova, Katerina
    et al.
    Grabic, Roman
    Fedorova, Ganna
    Fick, Jerker
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Cerveny, Daniel
    Kolarova, Jitka
    Turek, Jan
    Zlabek, Vladimir
    Randak, Tomas
    Bioaccumulation of psychoactive pharmaceuticals in fish in an effluent dominated stream2017In: Water Research, ISSN 0043-1354, E-ISSN 1879-2448, Vol. 124, p. 654-662Article in journal (Refereed)
    Abstract [en]

    The treated effluent from sewage treatment plants (STP) is a major source of active pharmaceutical ingredients (APIs) that enter the aquatic environment. Bioaccumulation of 11 selected psychoactive pharmaceuticals (citalopram, clomipramine, haloperidol, hydroxyzine, levomepromazine, mianserin, mirtazapine, paroxetine, sertraline, tramadol and venlafaxine) was examined in Zivny Stream (tributary of the Blanice River, the Czech Republic), which is a small stream highly affected by effluent from the Prachatice STP. Six of the 11 pharmaceuticals were detected in grab water samples and in passive samplers. All pharmaceuticals were found in fish exposed to the stream for a defined time. The organs with highest presence of the selected pharmaceuticals were the liver and kidney; whereas only one pharmaceutical (sertraline) was detected in the brain of exposed fish. Fish plasma and muscle samples were not adequate in revealing exposure because the number of hits was much lower than that in the liver or kidney. Using the criterion of a bioaccumulation factor (BAF) >= 500, citalopram, mianserin, mirtazapine and sertraline could be classified as potential bioaccumulative compounds. In combination, data from integrative passive samplers and fish liver or kidney tissue samples were complimentary in detection of target compounds and simultaneously helped to distinguish between bioconcentration and bioaccumulation.

  • 39.
    Haglund, Peter
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Spinnel, Erik
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    A Modular Approach to Pressurized Liquid Extraction with In-Cell Cleanup2011In: LC GC North America, ISSN 1527-5949, E-ISSN 1939-1889, no Suppl., p. 66-72Article in journal (Refereed)
    Abstract [en]

    A new concept for the extraction of solid samples has been developed. The popular pressurized liquid extraction (PLE) technique has been modified so that the extraction cell can be divided, which greatly increases the flexibility and versatility of this technique. The system uses simple adapters to couple commercially available extraction cells, which can be loaded with either sample or adsorbents. These segmented extraction cells make it possible to selectively retain analytes or matrix to achieve simultaneous extraction and cleanup or fractionation. The ultimate aim is to perform simultaneous extraction and cleanup and obtain a purified extract that is ready for instrumental analysis, all in line with current trends in analytical chemistry to automate and streamline the analytical procedures to reduce the analysis costs, solvent consumption, and manual labor, and increase the quality of analysis. Selected modes of operations are presented and a few recent environmental applications of modular PLE are reviewed.

  • 40.
    Haglund, Peter
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Spinnel, Erik
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    A Modular Approach to Pressurized Liquid Extraction with In-Cell Cleanup2010In: LC GC North America, ISSN 1527-5949, E-ISSN 1939-1889, Vol. 28, no 7, p. 544-+Article in journal (Refereed)
    Abstract [en]

    A new concept for the extraction of solid samples has been developed. The popular pressurized liquid extraction (PLE) technique has been modified so that the extraction cell can be divided, which greatly increases the flexibility and versatility of this technique. The system uses simple adapters to couple commercially available extraction cells, which can be loaded with either sample or adsorbents. These segmented extraction cells make it possible to selectively retain analytes or matrix to achieve simultaneous extraction and cleanup or fractionation. The ultimate aim is to perform simultaneous extraction and cleanup and obtain a purified extract that is ready for instrumental analysis, all in line with current trends in analytical chemistry to automate and streamline the analytical procedures to reduce the analysis costs, solvent consumption, and manual labor, and increase the quality of analysis. Selected modes of operations are presented and a few recent environmental applications of modular PLE are reviewed.

  • 41.
    Haglund, Peter
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Wiberg, Karin
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Determination of the gas chromatographic elution sequences of the (+)- and (-)-enantiomers of stable atropistomeric PCBs on Chirasil-Dex1996In: HRC Journal of High Resolution Chromatography, ISSN 0935-6304, E-ISSN 1521-4168, Vol. 19, no 7, p. 373-376Article in journal (Refereed)
    Abstract [en]

    Pure enantiomers of chiral (atropisomeric) polychlorinated biphenyls (PCBs) obtained by high-performance liquid chromatography were used to establish the gas chromatographic elution sequences of the (+)- and (−)-enantiomers of six PCB atropisomers on Chirasil-Dex. The elution order was found to be (−/+) for PCBs 84, 132, 136, and 176 and (+/−) for PCBs 135 and 174. The retention characteristics of all 19 tri- and tetra-ortho atropisomeric PCBs were also investigated. Nine of the atropisomers could be separated using this chiral selector. PCBs 95, 132, and 149 were completely resovled and PCBs 84, 91, 135, 136, 174, and 176 were partially separated (R = 0.7–0.9). All of the separated congeners are 2,3,6-substituted in at least one ring, and conversely – none of the congeners that lacks 2,3,6-substitution could be separated. Thus, chiral recognition and enantiomer separation seems to be strongly governed by 2,3,6-substitution.

  • 42.
    Harju, Mikael
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Bergman, Anders
    Olsson, Mats
    Roos, Anna
    Haglund, Peter
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Determination of atropisomeric and planar polychlorinated biphenyls, their enantiomeric fractions and tissue distribution in grey seals using comprehensive 2D gas chromatography2003In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1019, no 1-2, p. 127-142Article in journal (Refereed)
    Abstract [en]

    High prevalence of uterine occlusions and sterility is found among Baltic ringed and grey seal. Polychlorinated biphenyls (CBs) are suspected to be the main cause. The CB concentrations are higher in affected than in healthy animals, but the natural variation is considerable. Thus, it might be possible to assess the health status of seals by CB analysis. The ratios of chiral compounds (enantiomeric fractions (EFs)) such as atropisomeric CBs are of particular interest, since these may reflect differences in metabolic rates. An analytical procedure was developed and used to determine the levels of atropisomeric CBs, planar-CBs (WHO-PCBs) and total CBs in seals of different health status. Comprehensive 2D gas chromatography (GC×GC) was used to separate the target analytes from other CBs and interferences and a micro electron-capture detector (μECD) was used for detection. EFs of the atropisomeric CBs were difficult to determine as the levels were low and the interferences many. Two column combinations had to be used to avoid biased results—both had a chiral column as first-dimension column. The second-dimension column was coated with either a high-polarity cyanopropyl or a liquid crystal phase. EFs were determined for five atropisomeric CBs, i.e. CBs 91, 95, 132, 149 and 174. The results were verified by GC×GC–time-of-flight mass spectrometry (TOF-MS). Some atropisomeric CBs had EFs that deviated strongly from the racemic-mixture value. The deviations were larger in liver than blubber, which indicates enantioselective metabolism. However, there was no selective passage of the studied atropisomeric CBs across placenta and no selective blood–brain barrier. Similarly, no correlation between EFs and health status was observed, although there was a correlation between the total CB levels and health status.

  • 43. Harley, Steven J.
    et al.
    Ohlin, C. Andre
    Casey, William H.
    Geochemical kinetics via the Swift-Connick equations and solution NMR2011In: Geochimica et Cosmochimica Acta, ISSN 0016-7037, E-ISSN 1872-9533, Vol. 75, no 13, p. 3711-3725Article in journal (Refereed)
    Abstract [en]

    Signal analysis in Nuclear Magnetic Resonance spectroscopy is among the most powerful methods to quantify reaction rates in aqueous solutions. To this end, the Swift-Connick approximations to the Bloch-McConnell equations have been used extensively to estimate rate parameters for elementary reactions. The method is primarily used for O-17 NMR in aqueous solutions, but the list of geochemically relevant nuclei that can be used is long, and includes Si-29, Al-27, F-19, C-13 and many others of particular interest to geochemists. Here we review the derivation of both the Swift-Connick and Bloch-McConnell equations and emphasize assumptions and quirks. For example, the equations were derived for CW-NMR, but are used with modern pulse FT-NMR and can be applied to systems that have exchange rates that are shorter than the lifetime of a typical pulse. The method requires a dilute solution where the minor reacting species contributes a negligible amount of total magnetization. We evaluate the sensitivity of results to this dilute-solution requirement and also highlight the need for chemically well-defined systems if reliable data are to be obtained. The limitations in using longitudinal relaxation to estimate reaction rate parameters are discussed. Finally, we provide examples of the application of the method, including ligand exchanges from aqua ions and hydrolysis complexes, that emphasize its flexibility. Once the basic requirements of the Swift-Connick method are met, it allows geochemists to establish rates of elementary reactions. Reactions at this scale lend themselves well to methods of computational simulation and could provide key tests of accuracy. (C) 2011 Elsevier Ltd. All rights reserved.

  • 44. Hou, Song
    et al.
    Dlugogorski, Bogdan Z.
    Mackie, John C.
    Kennedy, Eric M.
    Jansson, Stina
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Altarawneh, Mohammednoor
    Oxidation of 4-bromo-4'-chlorobiphenyl, model species for forming mixed halogenated aromatic compounds2017In: International Journal of Environment and Pollution, ISSN 0957-4352, E-ISSN 1741-5101, Vol. 61, no 3-4, p. 243-260Article in journal (Refereed)
    Abstract [en]

    This contribution reports results from the gas-phase oxidation of 4-bromo-4'-chlorobiphenyl (4,4'-BCB) in order to fathom the formation of toxic species produced during the combustion of mixed halogenated aromatics. In their own right, mixed polybrominated/polychlorinated biphenyls (PXBs) represent a new class of environmental contaminants, recently detected in food and human tissues. Gas chromatography-quadrupole mass spectrometry (GC-QMS), gas chromatography-quadrupole time of flight mass spectrometry (GC-QTOFMS), Fourier transform infrared spectroscopy (FTIR) and ion chromatography (IC) served to analyse the volatile and semi-volatile organic compounds (V/SVOCs), including mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs), and gaseous products including HBr/HCl. The selection of non-ortho substituted PXB as a model species yields a large number of halogenated compounds, including monochloro- and monobromobenzene and higher halogenated benzenes and naphthalenes and derivatives of halogenated benzenes (such as 1-chloro-4-ethynylbenzene). We also detect small amounts of chlorinated and mixed halogenated dibenzofurans. The present study provides insights into the formation of several classes of halogenated and mixed-halogenated pollutants in combustion processes involving both bromine and chlorine sources, such as those of brominated flame retardants and PVC plastics.

  • 45.
    Jiang, Wen
    Umeå University, Faculty of Science and Technology, Chemistry.
    Zwitterionic Separation Materials for Liquid Chromatography and Capillary Electrophoresis: Synthesis, Characterization and Application for Inorganic Ion and Biomolecule Separations2003Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Liquid Chromatography (LC) and Capillary Electrophoresis (CE) are modern analytical techniques that play very important roles in many areas of modern science such as life science, biotechnology, biomedicine, environmental studies, and development of pharmaceutics. Even though these two techniques have existed and been subjected to studies for several decades, the developments of new separation materials for them are still very important till now in order to meet the different new demands for improvement from other disciplines in science.

    In this doctoral thesis, several novel covalently bonded sulfobetaine type zwitterionic separation materials are synthesized for the application in LC and CE. These materials carry both positively charged quaternary ammonium groups and negatively charged sulfonic groups, which result in a very low net surface charge compared to conventional separation materials with only anionic or cationic functional groups. Consequently, it is possible to employ these materials for separation of different ionic species under mild conditions. The surface properties have also been characterized, mainly by elemental analysis, sorption isotherm, ζ-potential measurements, and spectroscopic methods.

    By using packed zwitterionic columns for liquid chromatography, small inorganic anions or cations, and acidic or basic proteins can be independently and simultaneously separated in a single run using optimal sets of separation conditions. This is a unique property compared to conventional ionic separation material for LC. When fused silica capillaries coated with zwitterionic polymer are used for capillary electrophoresis, good separations can be achieved for solutes as different as inorganic anions, peptides, proteins, and tryptically digested proteins.

  • 46. Jogunola, Olatunde
    et al.
    Salmi, Tapio
    Leveneur, Sébastien
    Mikkola, Jyri-Pekka
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Åbo Akademi, Johan Gadolin Process Chemistry Centre, Laboratory of Industrial Chemistry and Reaction Engineering, Åbo/Turku, Finland.
    Complexation equilibria studies of alkyl formate hydrolysis in the presence of 1-butylimidazole2017In: Thermochimica Acta, ISSN 0040-6031, E-ISSN 1872-762X, Vol. 652, p. 62-68Article in journal (Refereed)
    Abstract [en]

    Formic acid production by ethyl or methyl formate hydrolysis was improved using 1-butylimidazole as a complexing agent. The chemical process involved both hydrolysis and complexation steps. The complexation equilibria were investigated by deriving theoretical equations using the equilibrium constant of the hydrolysis step, the apparent formation constant of the complexation process and the initial concentration of the complexing agent. The treatment of the experimental results within the experimental domain indicated that an equimolar amount of the acid and the base did not lead to the complex formation. Experimental observation suggested that the derived equation could be simplified by assuming that the stoichiometric coefficient of the complexing agent was 0.5. The apparent reaction enthalpy obtained from this equation was compared to the experimental one using a Tian-Calvet calorimeter and a good agreement was found between them. FTIR spectroscopy was used to confirm the existence of the complex between formic acid and 1-butylimidazole.

  • 47.
    Johansson, Anders
    et al.
    Umeå University, Faculty of Medicine, Department of Clinical Microbiology, Infectious Diseases. Umeå University, Faculty of Medicine, Department of Clinical Microbiology, Clinical Bacteriology.
    Petersen, Jeannine M
    Genotyping of Francisella tularensis, the causative agent of tularemia2010In: Journal of AOAC International, ISSN 1060-3271, E-ISSN 1944-7922, Vol. 93, no 6, p. 1930-1943Article in journal (Refereed)
    Abstract [en]

    Francisella tularensis is a facultative, intracellular, zoonotic pathogen and the causative agent of tularemia. Historically, F. tularensis has been subdivided into subspecies on the basis of phenotypic traits, including biochemical reactivity and virulence. More recently, a number of genotypic methods, ranging from relatively insensitive methods to full genome sequencing, have been used to investigate genetic diversity within F. tularensis. These analyses indicate that F. tularensis is a pathogen of low sequence diversity with pair-wise average nucleotide identities > 99.2% across subspecies. Nonetheless, genomic rearrangements and sequence deletions exist between and within F. tularensis subspecies, creating polymorphisms detectable by genotyping methods. Genetic subpopulations intermediate to the subspecies and strain level have been identified within F. tularensis subsp. tularensis and F. tularensis subsp. holarctica by several different typing methods. These genetic subpopulations have been associated with differences in disease severity, geographic distribution, and transmission patterns. For example, one F. tularensis subsp. tularensis subpopulation has been found to be significantly associated with mortality in humans. Additionally, genotypic analyses of Francisella spp. have provided information for use in the rational design of strain panels for validation of F. tularensis diagnostic tests. This review provides a guide to the various F. tularensis genotyping methods.

  • 48.
    Jonsson, Tobias
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Emteborg, Malin
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Irgum, Knut
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Heterocyclic compounds as catalysts in the peroxyoxalate chemiluminescence reaction of bis(2,4,6-trichlorophenyl)oxalate1998In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 361, no 3, p. 205-215Article in journal (Refereed)
    Abstract [en]

    Substituted imidazoles and leaving groups known from other areas of chemistry have been tested for catalytic efficiency in the peroxyoxalate chemiluminescence (PO-CL) reaction, using bis(2,4,6-trichlorophenyl)oxalate (TCPO) as reagent. Catalytic activity was found for 1,2,4-triazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole and 4,5-dichloroimidazole, while 2-mercaptoimidazole, 2-nitroimidazole, 4-nitroimidazole, benzimidazole, benzotriazole, thiazole, o-benzoic sulfimide, phthalimide, succinimide, 2(1H)-pyridone and 1,2,3-benzotriazine-4(3H)-one yielded no detectable chemiluminescence under the conditions used. None of the tested compounds was more efficient than imidazole in catalyzing the PO-CL reaction. Spectrophotometric measurements of the catalytic breakdown of TCPO showed that an intermediate was formed with almost all catalysts, and that intermediates that were more stable or present at lower concentration led to a reduced catalytic efficiency in the PO-CL reaction of TCPO.

  • 49.
    Jonsson, Tobias
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Irgum, Knut
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Very fast peroxyoxalate chemiluminescence1999In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 400, no 1-3, p. 257-264Article in journal (Refereed)
    Abstract [en]

    Peroxyoxalate chemiluminescence (PO-CL) detection offers an advantage in chromatographic detection, by the virtue of its multiple unique selectivities and high sensitivity. However, many of the analytical separation techniques available today require observation times in the millisecond range to preserve the band resolution, and as the reaction kinetics of the PO-CL reaction is considerably slower, extra flow elements are needed to observe the reaction in a time window at maximum emission intensity. Since these flow elements increase the complexity of the system and contribute to band-broadening, the rational way to adapt PO-CL detection to miniaturised separation systems is to speed up the reaction, so that it emits an initial burst of light within the acceptable detection time-frame. Although this may result in a lower overall quantum yield, the actual detection sensitivity could be equal to, or better than slower PO-CL systems. By making careful selections of oxalic reagent and catalyst(s) the reaction can be fine-tuned to maximise the intensity. In this work, the time-dependent light emission from the reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO) was studied under the catalytic influence of imidazole, 1,2,4-triazole, 4-dimethylaminopyridine (DMAP), and 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) in acetonitrile. Both DMAP and DBU accelerated the reaction substantially, but the best combination of reaction speed and intensity was found for a mixture of 0.5 mM DBU and 5 mM 1,2,4-triazole, which reached its maximum emission after only 40 ms and had an emission intensity comparable to that seen with 5 mM imidazole as catalyst.

  • 50.
    Karimpour, Masoumeh
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Multi-platform metabolomics assays to study the responsiveness of the human plasma and lung lavage metabolome2016Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Metabolomics as a field has been used to track changes and perturbations in the human body by investigating metabolite profiles indicating the change of metabolite levels over time and in response to different challenges. In this thesis work, the main focus was on applying multiplatform-metabolomics to study the human metabolome following exposure to perturbations, such as diet (in the form of a challenge meal) and exhaust emissions (air pollution exposure in a controlled setting). The cutting-edge analytical platforms used for this purpose were nuclear magnetic resonance (NMR), as well as gas chromatography (GC) and liquid chromatography (LC) coupled to mass spectrometry (MS). Each platform offered unique characterization features, allowing detection and identification of a specific range of metabolites. The use of multiplatform-metabolomics was found to enhance the metabolome coverage and to provide complementary findings that enabled a better understanding of the biochemical processes reflected by the metabolite profiles. Using non-targeted analysis, a wide range of unknown metabolites in plasma were identified during the postprandial stage after a well-defined challenge meal (in Paper I). In addition, a considerable number of metabolites were detected and identified in lung lavage fluid after biodiesel exhaust exposure compared to filtered air exposure (in Paper II). In parallel, using targeted analysis, both lung lavage and plasma fatty acid metabolites were detected and quantified in response to filtered air and biodiesel exhaust exposure (in Paper III and IV).

    Data processing of raw data followed by data analysis, using both univariate and multivariate methods, enabled changes occurring in metabolites levels to be screened and investigated. For the initial pilot postprandial study, the aim was to investigate the plasma metabolome response after a well-defined meal during the postprandial stage for two types of diet. It was found that independent of the background diet type, levels of metabolites returned to their baseline levels after three hours. This finding was taken into consideration for the biodiesel exhaust exposures studies, designed to limit the impact of dietary effects. Both targeted and non-targeted approaches resulted in important findings. For instance, different metabolite profiles were detected in bronchial wash (BW) compared to bronchoalveolar lavage (BAL) fluid with mainly NMR and LC-MS. Furthermore, biodiesel exhaust exposure resulted in different metabolite profiles as observed by GC-MS, especially in BAL. In addition, fatty acid metabolites in BW, BAL, and plasma were shown to be responsive to biodiesel exhaust exposure, as measured by a targeted LC-MS/MS protocol. In summary, the new analytical methods developed to investigate the responsiveness of the human plasma and lung lavage metabolome proved to be useful in an analytical perspective, and provided important biological findings. However, further studies are needed to validate these results.

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