| 1. |
- Bixby, H., et al.
(författare)
-
Rising rural body-mass index is the main driver of the global obesity epidemic in adults
- 2019
-
Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 569:7755, s. 260-4
-
Tidskriftsartikel (refereegranskat)abstract
- Body-mass index (BMI) has increased steadily in most countries in parallel with a rise in the proportion of the population who live in cities(.)(1,2) This has led to a widely reported view that urbanization is one of the most important drivers of the global rise in obesity(3-6). Here we use 2,009 population-based studies, with measurements of height and weight in more than 112 million adults, to report national, regional and global trends in mean BMI segregated by place of residence (a rural or urban area) from 1985 to 2017. We show that, contrary to the dominant paradigm, more than 55% of the global rise in mean BMI from 1985 to 2017-and more than 80% in some low- and middle-income regions-was due to increases in BMI in rural areas. This large contribution stems from the fact that, with the exception of women in sub-Saharan Africa, BMI is increasing at the same rate or faster in rural areas than in cities in low- and middle-income regions. These trends have in turn resulted in a closing-and in some countries reversal-of the gap in BMI between urban and rural areas in low- and middle-income countries, especially for women. In high-income and industrialized countries, we noted a persistently higher rural BMI, especially for women. There is an urgent need for an integrated approach to rural nutrition that enhances financial and physical access to healthy foods, to avoid replacing the rural undernutrition disadvantage in poor countries with a more general malnutrition disadvantage that entails excessive consumption of low-quality calories.
|
|
| 2. |
|
|
| 3. |
|
|
| 4. |
- Patriarca, Claudia, et al.
(författare)
-
Investigating the Ionization of Dissolved Organic Matter by Electrospray
- 2020
-
Ingår i: Analytical Chemistry. - : American Chemical Society (ACS). - 0003-2700 .- 1520-6882. ; 92:20, s. 14210-14218
-
Tidskriftsartikel (refereegranskat)abstract
- Electrospray ionization (ESI) operating in the negative mode coupled to high-resolution mass spectrometry is the most popular technique for the characterization of dissolved organic matter (DOM). The vast molecular heterogeneity and the functional group diversity of this complex mixture prevents the efficient ionization of the organic material by a single ionization source, so the presence of uncharacterized material is unavoidable. The extent of this poorly ionizable pool of carbon is unknown, is presumably variable between samples, and can only be assessed by the combination of analysis with a uniform detection method. Charged aerosol detection (CAD), whose response is proportional to the amount of nonvolatile material and is independent from the physicochemical properties of the analytes, is a suitable candidate. In this study, a fulvic acid mixture was fractionated and analyzed by high-pressure liquid chromatography–mass spectrometry in order to investigate the polarity and size distributions of highly and poorly ionizable material in the sample. Additionally, DOM samples of terrestrial and marine origins were analyzed to evaluate the variability of these pools across the land–sea aquatic continuum. The relative response factor values indicated that highly ionizable components of aquatic DOM mixtures are more hydrophilic and have lower molecular weight than poorly ionizable components. Additionally, a discrepancy between the samples of terrestrial and marine origins was found, indicating that marine samples are better represented by ESI than terrestrial samples, which have an abundant portion of hydrophobic poorly ionizable material.
|
|
| 5. |
- Rydfjord, Jonas, et al.
(författare)
-
Decarboxylative Palladium(II)-Catalyzed Synthesis of Aryl Amidines from Aryl Carboxylic Acids : Development and Mechanistic Investigation
- 2013
-
Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 19:41, s. 13803-13810
-
Tidskriftsartikel (refereegranskat)abstract
- A fast and convenient synthesis of aryl amidines starting from carboxylic acids and cyanamides is reported. The reaction was achieved by palladium(II)-catalysis in a one-step microwave protocol using [Pd(O2CCF3)(2)], 6-methyl-2,2-bipyridyl and trifluoroacetic acid (TFA) in N-methylpyrrolidinone (NMP), providing the corresponding aryl amidines in moderate to excellent yields. The protocol is very robust with regards to the cyanamide coupling partner but requires electron-rich ortho-substituted aryl carboxylic acids. Mechanistic insight was provided by a DFT investigation and direct ESI-MS studies of the reaction. The results of the DFT study correlated well with the experimental findings and, together with the ESI-MS study, support the suggested mechanism. Furthermore, a scale-out (scale-up) was performed with a non-resonant microwave continuous-flow system, achieving a maximum throughput of 11mmolh(-1) by using a glass reactor with an inner diameter of 3mm at a flow rate of 1mLmin(-1).
|
|
| 6. |
- Santos-Neto, Alvaro J., et al.
(författare)
-
Simultaneous analysis of five antidepressant drugs using direct injection of biofluids in a capillary restricted-access media-liquid chromatography-tandem mass spectrometry system
- 2008
-
Ingår i: Journal of Chromatography A. - : Elsevier BV. - 0021-9673 .- 1873-3778. ; 1189:1-2, s. 514-522
-
Tidskriftsartikel (refereegranskat)abstract
- Direct analysis, with minimal sample pretreatment, of antidepressant drugs, fluoxetine, imipramine, desipramine, amitriptyline, and nortriptyline in biofluids was developed with a total run time of 8 min. The setup consists of two HPLC pumps, injection valve, capillary RAM-ADS-C18 pre-column and a capillary analytical C 18 column connected by means of a six-port valve in backflush mode. Detection was performed with ESI-MS/MS and only 1 mu m of sample was injected. Validation was adequately carried out using FLU-d(5) as internal standard. Calibration curves were constructed under a linear range of 1-250 ng mL(-1) in plasma, being the limit of quantification (LOQ), determined as 1 ng mL(-1), for all the analytes. With the described approach it was possible to reach a quantified mass sensitivity of 0.3 pg for each analyte (equivalent to 1.1-1.3 fmol), translating to a lower sample consumption (in the order of 103 less sample than using conventional methods).
|
|
| 7. |
- Allard, Erik, et al.
(författare)
-
Comparing capillary electrophoresis : mass spectrometry fingerprints of urine samples obtained after intake of coffee, tea, or water.
- 2008
-
Ingår i: Analytical Chemistry. - : American Chemical Society (ACS). - 0003-2700 .- 1520-6882. ; 80:23, s. 8946-8955
-
Tidskriftsartikel (refereegranskat)abstract
- Metabolomic fingerprinting is a growing strategy for characterizing complex biological samples without detailed prior knowledge about the metabolic system. A two-way analysis system with liquid separation and mass spectrometric detection provides detail-rich data suitable for such fingerprints. As a model study, human urine samples, obtained after intake of coffee, tea, or water, were analyzed with capillary electrophoresis electrospray ionization time-of-flight mass spectrometry (CE−ESI-TOF-MS). In-house-developed software (in Matlab) was utilized to manage and explore the large amount of data acquired (230 CE−MS runs, each with 50−100 million nonzero data points). After baseline and noise reduction, followed by suitable binning in time and m/z, the data sets comprised 9 and 14 million data points in negative and positive ESI mode, respectively. Finally, a signal threshold was applied, further reducing the number to about 100 000 data points per data set. A set of interactive exploratory tools, utilizing principal component analysis (PCA) and analysis of variance (ANOVA) results based on a general linear model, facilitated visual interpretation with score plots (for group assessment) and differential fingerprints (for “hot spot” detection). In the model study highly significant differences due to beverage intake were obtained among the 10 first principal components (p < 10−6 for two of the components in both ESI modes). Especially, the contrasts between “coffee” and “tea or water” indicated several “hot spots” with highly elevated intensities (e.g., for uncharged masses 93, 94, 109, 119, 123, 132, 148, 169, 178, 187, 190, and 193) suitable for further analysis, for example, with tandem MS.
|
|
| 8. |
- Andaloussi, Mounir, et al.
(författare)
-
Microwave-promoted palladium(II)-catalyzed C-P bond formation by using arylboronic acids or aryltrifluoroborates.
- 2009
-
Ingår i: Chemistry - A European Journal. - Weinheim : Wiley-VCH Verlag GmbH. - 0947-6539 .- 1521-3765. ; 15:47, s. 13069-13074
-
Tidskriftsartikel (refereegranskat)abstract
- The first Pd-II-catalyzed P arylation has been performed by using palladium acetate, the rigid bidentate ligand dmphen (dmphen=2,9-dimethyl-1,10-phenanthroline), and without the addition of base or acid. Couplings of arylboronic acids or aryl trifluoroborates with H-phosphonate dialkyl esters were conducted in 30 min with controlled microwave (MW) heating under non-inert conditions. Aryl phosphites were also synthesized at room temperature with atmospheric air as the sole reoxidant. The arylated phosphonates were isolated in 44-90% yields. The excellent chemoselectivity of the method was illustrated in the synthesis of a Mycobacterium tuberculosis glutamine synthetase (MTB-GS) inhibitor. Online ESIMS was used to detect cationic palladium species in ongoing reactions directly, and a catalytic cycle has been proposed based on these results.
|
|
| 9. |
- Arapitsas, Panagiotis, et al.
(författare)
-
Characterisation of anthocyanins in red cabbage using high resolution liquid chromatography coupled with photodiode array detection and electrospray ionization-linear ion trap mass spectrometry.
- 2008
-
Ingår i: Food Chemistry. - : Elsevier BV. - 0308-8146 .- 1873-7072. ; 109:1, s. 219-226
-
Tidskriftsartikel (refereegranskat)abstract
- The aim of this work was to analyse and tentatively identify anthocyanin species in red cabbage using HPLC/DAD-ESI/Qtrap MS. The extraction was realized by using a pressurized liquid technique and the separation of the pigments was achieved by a high resolution liquid chromatography system with a 1.8 mu m particles C-18 column. Photodiode array detection was employed to determine the UV/Vis spectral characteristic of the pigments. Electrospray ionization-linear ion trap mass spectrometry allowed the specific determination of the fragmentation patterns of the anthocyanins, by performing different ion scan modes. Twenty four anthocyanins were separated and identified, all having cyanidin as aglycon, represented as mono- and/or di-glycoside, and acylated, or not, with aromatic and aliphatic acids. Nine anthocyanins were identified for the first time in red cabbage.
|
|
| 10. |
- Axén, Jakob, et al.
(författare)
-
An investigation of peak-broadening effects arising when combining CE with MS.
- 2007
-
Ingår i: Electrophoresis. - : Wiley. - 0173-0835 .- 1522-2683. ; 28:18, s. 3207-3213
-
Tidskriftsartikel (refereegranskat)abstract
- In this study, peak-broadening effects caused by nebulizing gas flow and lack of temperature control have been investigated for separation capillaries with three different inner diameters. The study was performed with serial UV/ESI-MS detection in an effort to distinguish between peak broadening arising in the separation and peak broadening arising in the ion source. The nebulizing gas was found to significantly affect both migration time and separation efficiency when using capillaries with 50 and 75 µm id. If the nebulizing gas is on during injection, the injection volume increases to such an extent that significant peak broadening is induced. Reducing the id to 25 µm minimizes the parabolic flow induced by the nebulizing gas. Results indicate that the nebulizing gas pressure can be optimized to minimize peak broadening in the ion source. A decrease in detection sensitivity, possibly related to the orthogonal design of the interface, was observed when the nebulizing gas pressure was increased. A tapered capillary tip was found to provide superior separation efficiency as well as sensitivity.
|
|
| 11. |
- Axén, Jakob, et al.
(författare)
-
Efforts to improve detection sensitivity for capillary electrophoresis coupled to atmospheric pressure photoionization mass spectrometry.
- 2010
-
Ingår i: Rapid Communications in Mass Spectrometry. - : John Wiley & Sons Ltd. - 0951-4198 .- 1097-0231. ; 24:9, s. 1260-1264
-
Tidskriftsartikel (refereegranskat)abstract
- Electrospray ionization performs best with volatile buffers. However, generally the best separation performance for capillary electrophoresis (CE) is achieved with non-volatile buffers. Hyphenation of CE with mass spectrometry (MS) utilizing atmospheric pressure photoionization (APPI) enables use of a wider range of separation buffers without compromising detection sensitivity. As APPI is considered to be mass flow sensitive, the use of a larger inner diameter separation capillary (75 microm) allows larger volumes to be injected, without decreased separation performance, thus providing improved sensitivity (approx. a factor of 10), compared to the use of a 25 microm capillary. However, nebulizing gas flow and position of capillary tip in the sprayer have to be carefully optimized to prevent excessive band broadening. Further improvement in sensitivity (approx. a factor of 2) was obtained by decreasing the distance between the sprayer and ionization region, indicating that a specially designed CE/APPI-MS interface for low flow rates will be favourable.
|
|
| 12. |
|
|
| 13. |
- Bergvall, Ulrika A., et al.
(författare)
-
Anti-browsing effects of birch bark extract on fallow deer
- 2013
-
Ingår i: European Journal of Forest Research. - : Springer Science and Business Media LLC. - 1612-4669 .- 1612-4677. ; 132:5-6, s. 717-725
-
Tidskriftsartikel (refereegranskat)abstract
- A major problem within forest industry is unwanted browsing on seedlings from mammalian herbivores. The aim of this study was to evaluate the effects of birch bark extracts as repellents towards fallow deer. Birch bark was extracted in a conventional way with ethanol as solvent at ambient temperature and with a new method, liquid CO2 extraction. An analysis of the ethanol-extracted birch bark showed that it contained large amounts of terpenoids, of which the most abundant was betulin. In seven different treatment trials, we used 15 individually handled fallow deer. To investigate the binary taste preferences, birch bark extract was added to food and presented in two bowls in typical two-choice tests. We found that the amount of a food type consumed during a trial and the number of shifts between food bowls were dependent on the amount of the birch extract the food contained. Concentrations of above 1 % by dry weight of birch extract acted as a repellent. In addition, such concentrations produced shorter feeding bouts by a greater willingness to change bowls. Therefore, our conclusion is that birch bark extract acts as a repellent towards fallow deer and is therefore likely to act as a repellent against other deer species. In addition, we show that birch bark extract produced by the new and more environmentally sustainable method employing liquid CO2 mixed with ethanol has the same repellent effect as the traditional ethanol extraction.
|
|
| 14. |
- Bunrit, Anon, et al.
(författare)
-
A General Route to beta-Substituted Pyrroles by Transition-Metal Catalysis
- 2016
-
Ingår i: Journal of Organic Chemistry. - : American Chemical Society (ACS). - 0022-3263 .- 1520-6904. ; 81:4, s. 1450-1460
-
Tidskriftsartikel (refereegranskat)abstract
- An atom-efficient route to pyrroles substituted in the beta-position has been achieved in four high yielding steps by a combination of Pd, Ru, and Fe catalysis with only water and ethene as side-products. The reaction is general and gives pyrroles substituted in the beta-position with linear and branched alkyl, benzyl, or aryl groups in overall good yields. The synthetic route includes a Pd-catalyzed monoallylation step of amines with substituted allylic alcohols that proceeds to yield the monoallylated products in moderate to excellent yields. In a second step, unsymmetrical diallylated aromatic amines are generated from the reaction of a second allylic alcohol with high selectivity in moderate to good yields by control of the reaction temperature. Ru-catalyzed ring-closing metathesis performed on the diallylated aromatic amines yields the pyrrolines substituted in the beta-position in excellent yields. By addition of ferric chloride to the reaction mixture, a selective aromatization to yield the corresponding pyrroles substituted in the beta-position was achieved. A reaction mechanism involving a palladium hydride, generated from insertion of palladium to O-H of an allyl alcohol, that is responsible for the C-O bond cleavage to generate the pi-allyl intermediate is proposed.
|
|
| 15. |
- Bunrit, Anon, et al.
(författare)
-
Brønsted Acid-Catalyzed Intramolecular Nucleophilic Substitution of the Hydroxyl Group in Stereogenic Alcohols with Chirality Transfer
- 2015
-
Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 137:14, s. 4646-4649
-
Tidskriftsartikel (refereegranskat)abstract
- The hydroxyl group of enantioenriched benzyl, propargyl, allyl, and alkyl alcohols has been intramolecularly displaced by uncharged O-, N-, and S-centered nucleophiles to yield enantioenriched tetrahydrofuran, pyrrolidine, and tetrahydrothiophene derivatives with phosphinic acid catalysis. The five-membered heterocyclic products are generated in good to excellent yields, with high degree of chirality transfer, and water as the only side-product. Racemization experiments show that phosphinic acid does not promote S(N)1 reactivity. Density functional theory calculations corroborate a reaction pathway where the phosphinic acid operates as a bifunctional catalyst in the intramolecular substitution reaction. In this mechanism, the acidic proton of the phosphinic acid protonates the hydroxyl group, enhancing the leaving group ability. Simultaneously, the oxo group of phosphinic acid operates as a base abstracting the nucleophilic proton and thus enhancing the nucleophilicity. This reaction will open up new atom efficient techniques that enable alcohols to be used as nucleofuges in substitution reactions in the future.
|
|
| 16. |
|
|
| 17. |
- Bäckström, Daniel, et al.
(författare)
-
Multivariate comparison between peptide mass fingerprints obtained by liquid chromatography-electrospray ionization-mass spectrometry with different trypsin digestion procedures
- 2007
-
Ingår i: Journal of Chromatography A. - : Elsevier BV. - 0021-9673 .- 1873-3778. ; 1171:1-2, s. 69-79
-
Tidskriftsartikel (refereegranskat)abstract
- Peptide mass fingerprints were obtained for three different proteins using three different digestion procedures in triplicates with liquid chromatography coupled to electrospray ionization mass spectrometry. For each protein the results were compared with multivariate data analysis (cluster analysis, kernel principal component analysis) and pair-wise contrast evaluation. Clear systematic differences between the digestion procedures were established for all the proteins. The visual presentation of the pair-wise differences between procedures could to some extent be related to the protein fragments, although the main objective was to identify m/z and retention regions in the original peptide maps that should be subject to further exploration.
|
|
| 18. |
- Bökman, C.Fredrik, et al.
(författare)
-
A Setup for the Coupling of a Thin-Layer Electrochemical Flow Cell to Electrospray Mass Spectrometry
- 2004
-
Ingår i: Analytical Chemistry. ; 76:7, s. 2017-2024
-
Tidskriftsartikel (refereegranskat)abstract
- A novel setup for the coupling of commercially available thin-layer cell to electrospray mass spectrometry (ESI-MS) which allows the elctrochemical reactions at the counter electrode to be straightforwardly separated from the flow into the mass spectrometer has been developed. In this way interferences from reaction products formed at the counter electrode can be minimized. This reduces the risk of changes in the mass spectra as a result of electrochemical reactions in the solution. The described setup also enables the working electrode to be positioned close to the electrospray (ESI) emitter without the need for a grounding point or a long transfer line between the electrochemical cell and the electrospray emitter. By decoupling the electrochemical reactions in the flow cell and those in the electrospray emitter, improved facilities for studies of electrochemical reactions are obtained through a better control of the potential of the working electrode. The setup has been used to study the oxidation of a drug (Olsalazine), which previously has been found to involve chemical follow-up reactions. It is also demonstrated that uncharged thiols can be detected in ESI-MS after spontaneous adsorption on a gold working electrode, followed by oxidative desorption to yield sulfinates or sulfonates. This adsorption and potential-controlled desorption has been used for the preconcentration of micromolar concentrations of 1-hexanethiol as well as for desalting of solutions containing micromolar concentrations of thiols. The results indicate that the present on-line coupling of an electrochemical cell to ESI-MS provides promising possibilities for sample preconcentration, matrix exchange (including desalting), and ionization of neutral compounds, such as thiols.
|
|
| 19. |
- Bökman, C.F., et al.
(författare)
-
Relating chromatographic retention and electrophoretic mobility to the ion distribution within electrosprayed droplets
- 2006
-
Ingår i: Journal of the American Society for Mass Spectrometry. - : American Chemical Society (ACS). - 1044-0305 .- 1879-1123. ; 17:3, s. 318-324
-
Tidskriftsartikel (refereegranskat)abstract
- Ions that are observed in a mass spectrum obtained with electrospray mass spectrometry can be assumed to originate preferentially from ions that have a high distribution to the surface of the charged droplets. In this study, a relation between chromatographic retention and electrophoretic mobility to the ion distribution (derived from measured signal intensities in mass spectra and electrospray current) within electrosprayed droplets for a series of tetraalkylammonium ions, ranging from tetramethyl to tetrapentyl, is presented. Chromatographic retention in a reversed-phase system was taken as a measure of the analyte's surface activity, which was found to have a large influence on the ion distribution within electrosprayed droplets. In addition, different transport mechanisms such as electrophoretic migration and diffusion can influence the surface partitioning coefficient. The viscosity of the solvent system is affected by the methanol content and will influence both diffusion and ion mobility. However, as diffusion and ion mobility are proportional to each other, we have, in this study, chosen to focus on the ion mobility parameter. It was found that the influence of ion mobility relative to surface activity on the droplet surface partitioning of analyte ions decreases with increasing methanol content. This effect is most probably coupled to the decrease in droplet size caused by the decreased surface tension at increasing methanol content. The same observation was made upon increasing the ionic strength of the solvent system, which is also known to give rise to a decreased initial droplet size. The observed effect of ionic strength on the droplet surface partitioning of analyte ions could also be explained by the fact that at higher ionic strength, a larger number of ions are initially closer to the droplet surface and, thus, the contribution of ionic transport from the bulk liquid to the liquid/air surface interface (jet and droplet surface), attributable to migration or diffusion will decrease.
|
|
| 20. |
- Co, Michelle, 1975-, et al.
(författare)
-
Degradation effects in the extraction of antioxidants from birch bark using water at elevated temperature and pressure
- 2012
-
Ingår i: Analytica Chimica Acta. - : Elsevier BV. - 0003-2670 .- 1873-4324. ; 716, s. 40-48
-
Tidskriftsartikel (refereegranskat)abstract
- Experiments with birch bark samples have been carried to enable a distinction between extraction and degradation effects during pressurised hot water extraction. Two samples, E80 and El 80, contained birch bark extracts obtained after extraction at 80 and 180 degrees C for up to 45 min, respectively. Two other samples, P80 and P180, were only extracted for 5 min at the two temperatures and were thereafter filtered and hydrothermally treated at 80 and 180 degrees C, respectively. During the latter treatment, samples were collected at different times to assess the stability of the extracted compounds. An offline DPPH (2,2-diphenyl-1-picrylhydrazyl) assay, as well as a high performance liquid chromatographic separation coupled to an electrochemical detector, were used to determine the antioxidant capacity of the processed samples. The results obtained with the different techniques were compared to assess the yield of the extraction and degradation processes. In addition, an online hyphenated system comprising high performance liquid chromatography coupled to diode-array; electrochemical; and tandem mass spectrometric detection (HPLC-DAD-ECD-MS/MS) was used to study the compositions of the extracts in more detail. The results for the samples processed at 80 degrees C showed that the extraction reached a steady-state already after 5 min, and that the extracted compounds were stable throughout the entire extraction process. Processing at 180 degrees C, on the other hand, gave rise to partly degraded extracts with a multitude of peaks in both the diode array and electrochemical detectors, and a higher antioxidant capacity compared to for the extracts obtained at 80 degrees C. It is concluded that HPLC-DAD-ECD is a more appropriate technique for the determination of antioxidants than the DPPH assay. The mass spectrometric results indicate that one of the extracted antioxidants, catechin, was isomerised to its diastereoisomers; (+)-catechin, (-)-catechin, (+)-epicatechin, and (-)-epicatechin.
|
|
| 21. |
- Co, Michelle, 1975-, et al.
(författare)
-
Extraction of Antioxidants from Spruce (Picea abies) Bark using Eco-Friendly Solvents
- 2012
-
Ingår i: Phytochemical Analysis. - : Wiley-Blackwell. - 0958-0344 .- 1099-1565. ; 23:1, s. 1-11
-
Tidskriftsartikel (refereegranskat)abstract
- Introduction-Antioxidants are known to avert oxidation processes and they are found in trees and other plant materials. Tree bark is a major waste product from paper pulp industries; hence it is worthwhile to develop an extraction technique to extract the antioxidants.Objective- To develop a fast and environmentally sustainable extraction technique for the extraction of antioxidants from bark of spruce (Picea abies) and also to identify the extracted antioxidants that are abundant in spruce bark.Methodology- A screening experiment that involved three different techniques, was conducted to determine the best technique to extract antioxidants.The antioxidant capacity of the extracts was determined with DPPH (2,2-diphenyl-2’-picrylhydrazyl) assay. Pressurised fluid extraction (PFE) turned out to be the best technique and a response surface design was therefore utilised to optimise PFE. Furthermore, NMR and HPLC-DAD-MS/MS were applied to identify the extracted antioxidants.Results- PFE using water and ethanol as solvent at 160 and 180°C, respectively, gave extracts of the highest antioxidant capacity. Stilbene glucosides such as isorhapontin, piceid and astringin were identified in the extracts.Conclusion-The study has shown that PFE is a fast and environmentally sustainable technique, using water and ethanol as solvent for the extraction of antioxidants from spruce bark.
|
|
| 22. |
- Co, Michelle, 1975-
(författare)
-
Pressurised Fluid Extraction of Bioactive Species in Tree Barks : Analysis using Hyphenated Electrochemical Mass Spectrometric Detection
- 2010
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Analytical chemistry has developed throughout time to meet current needs. At present, the interest in biorefinery is growing, due to environmental awareness and the depletion of fossil resources. Biomass from agricultural and forestry industries has proven to be excellent raw material for different processes. Biorefinering valuable species such as bioactive species from biomass, without compromising the primary process of the biomass is highly desirable. Pressurised fluid extraction (PFE) using water and ethanol as a solvent was developed for extracting betulin from birch (Betula pendula) bark. Apart from betulin, stilbene glucosides such as astringin, isorhapontin and picied were also extracted from spruce (Picea abies) using PFE. PFE is an advanced technique that extracts at temperatures above the solvent’s atmospheric boiling point. The applied pressure in PFE is mainly to maintain the liquid state of the extraction solvent. Parameters such as type of solvent, temperature, and time affect the extraction selectivity and efficiency. Therefore it is necessary to comprehend these parameters in order to optimise extraction. The DPPH (1,1-diphenyl-2-picrylhydrazyl) assay was used to determine the antioxidant capacity and activity of the obtained bioactive species. The results showed high antioxidant capacity in bioactive species that were extracted at an elevated temperature, 180°C. Extraction and degradation occur simultaneously during the extraction. Hence, it is crucial to separate these two processes in order to obtain the actual value. An online hyphenated system of chromatographic separation electrochemical mass spectrometric detection was developed (LC-DAD-ECD-MS/MS). The electrochemical detector facilitates real-time monitoring of the antioxidant capacity and activity of each antioxidant and its oxidation products. This developed LC-DAD-ECD-MS/MS method enabled rapid screening of antioxidants and created a fingerprint map for their oxidation products. Characterisation and molecular elucidation of bioactive species were also performed. Degradation of bioactive species was investigated with the said online system and birch bark extract was compared with birch bark extracts that were hydrothermally treated. The obtained results showed some degradation of antioxidants at 180°C. In summary, the aim of this thesis was to develop analytical methods integrated with sustainable chemistry for extraction of bioactive species in biomass from the forestry industry. A novel online system using selective and sensitive detectors such as diode-array, electrochemical, and tandem mass spectrometry was developed to rapidly determine the antioxidant capacity and activity of antioxidants. Furthermore, tandem mass spectrometry enables identification of unknown bioactive species without the need of reference samples.
|
|
| 23. |
- Co, Michelle, et al.
(författare)
-
Pressurized liquid extraction of betulin and antioxidants from birch bark
- 2009
-
Ingår i: Green Chemistry. - : The Royal Society of Chemistry. - 1463-9262 .- 1463-9270. ; 11:5, s. 668-674
-
Tidskriftsartikel (refereegranskat)abstract
- Pressurized hot (subcritical) water and ethanol were used to extract betulin and antioxidants from birch bark. Betulin was found to be the major compound (around 26% (w/w)), which was able to be extracted with ethanol (120 degrees C, 50 bar, 15 minutes) but not with water at any of the temperatures tested (40-180 degrees C, 50 bar). The obtained extraction result for betulin is supported by theoretical solvation parameter calculations. Furthermore, high antioxidant activity of the extract was obtained using both ethanol and water as solvent. The antioxidant activity, as determined by a DPPH (2,2-diphenyl-1-picrylhydrazyl) assay, was found to be highest for the water extract of finely ground bark and it markedly increased with elevated extraction temperatures (90-180 degrees C). To elucidate if this was due to increased extraction efficiency or chemical reactions, a set of experiments was performed in which the samples were pre-treated with water at different temperatures before extraction. Results from liquid chromatography showed some differences in molecular composition between samples pre-treated at ambient and 180 degrees C, respectively. However, more detailed studies have to be performed to distinguish between hot-water extraction and reaction kinetics.
|
|
| 24. |
|
|
| 25. |
- De Brabandere, Heidi, 1980-
(författare)
-
Organic Phosphorus Compounds in Aquatic Sediments : Towards Molecular Identification with Mass Spectrometry
- 2008
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Phosphorus (P) regulates trophic status in most aquatic systems. However, only bioavailable P contributes to primary production. In most lakes and shallow seas, mineralisation of sediment P into its bioavailable form and its release to the water column is important for maintaining primary production. Sediment organic P forms a substantial proportion of this P to be mineralised and can originate from different sources on land (farmland, forests, etc.) or from primary production in the lake. These organic P forms can thus be expected to have differing composition, degradability and recyclable P content. Knowledge of the chemical structure of sediment organic P compounds is scarce, mainly due to lack of appropriate analytical techniques. The commonly used 31P-nuclear magnetic resonance (31P-NMR) technique, only identifies P binding groups, so a mass spectrometric (MS) analysis method was developed that allows individual sediment organic P compounds to be identified. EDTA as pre-extractant resulted in the highest P yield in subsequent NaOH extraction. Extracted organic P compound groups were identified using 31P-NMR. For identification of specific P compounds with MS, a sample preparation method prior to electrospray tandem mass spectrometry (ESI-MS/MS) analysis was developed. Liquid chromatography (LC) with porous graphitic carbon prior to ESI-MS/MS enhanced sensitivity and selectivity, enabling several of the ions detected to be identified as nucleotides. 31P-NMR analysis showed P monoesters to be the most stabile P compounds throughout a lake sediment profile. The developed LC-ESI-MS/MS analysis method revealed that some monoester-P (nucleotides) were labile, while other P compounds increased in concentration with Baltic Sea sediment depth and were therefore considered stabile. Differences in patterns of P compounds detected were also shown depending on catchment characteristics in relation to Baltic Sea sediment age. For cost-effective management of eutrophication, knowledge of the sources of degradable organic P forms, contributing to internal loading, is needed. This thesis showed the developed LC-ESI-MS/MS analysis method to be a powerful analytical tool for this purpose.
|
|
| 26. |
- De Brabandere, Heidi, et al.
(författare)
-
Screening for Organic Phosphorus Compounds in Aquatic Sediments by Liquid Chromatography Coupled to ICP-AES and ESI-MS/MS
- 2008
-
Ingår i: Analytical Chemistry. - : American Chemical Society (ACS). - 0003-2700 .- 1520-6882. ; 80:17, s. 6689-6697
-
Tidskriftsartikel (refereegranskat)abstract
- The structures of organic phosphorous (P) compounds in aquatic sediments are to a large extent unknown although these compounds are considered to play an important role in regulating lake trophic status. To enhance identification of these compounds, a liquid chromatography (LC) method for their separation was developed. The stationary phase was porous graphitic carbon (PGC), and the mobile phases used in the gradient elution were compatible with both inductive coupled plasma atomic emission spectroscopy (ICP-AES) and electrospray ionization tandem mass spectrometry (ESI-MS/MS). With LC-ICP-AES, eight different P containing peaks could be observed in the P chromatogram indicating that at least eight different P compounds were separated. With the setup of an information dependent acquisition (IDA) with ESI-MS/MS, the mass over charge (m/z) of compounds containing a phosphate group (H2PO3−, m/z 97) could be measured and further fragmentation experiments gave additional information on the structure of almost 40 separated P compounds, several were verified to be nucleotides. ICP-AES was very suitable in the development of the LC method and allowed screening and quantification of P compounds. The presented LC-ESI-MS/MS technique was able to identify several sediment organic P compounds.
|
|
| 27. |
- De Brabandere, Heidi, et al.
(författare)
-
Sediment extraction and clean-up for organic phosphorus analysis by electrospray ionization tandem mass spectrometry
- 2008
-
Ingår i: Talanta. - : Elsevier BV. - 0039-9140 .- 1873-3573. ; 74:5, s. 1175-1183
-
Tidskriftsartikel (refereegranskat)abstract
- 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, 31P-nuclear magnetic resonance spectroscopy (31P 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 31P 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.
|
|
| 28. |
- Fardost, Ashkan, et al.
(författare)
-
Palladium(II)-Catalyzed Decarboxylative Heck Arylations of Acyclic Electron-Rich Olefins with Internal Selectivity
- 2014
-
Ingår i: Advanced Synthesis and Catalysis. - : Wiley. - 1615-4150 .- 1615-4169. ; 356:4, s. 870-878
-
Tidskriftsartikel (refereegranskat)abstract
- Despite the recent emergence of decarboxylative CC bond forming reactions, methodologies providing internally arylated electron-rich olefins are still lacking. We herein report on palladium(II)-catalyzed decarboxylative Heck arylations of linear electron-rich olefins with excellent selectivity for the internal position. The method allows a variety of electron-rich linear olefins to undergo arylation with ortho-functionalized aromatic carboxylic acids, including heterocycles. The reaction mechanism has been explored with ESI-MS studies to confirm previous findings, and to reveal the formation of a highly stable palladium complex as a result of the Heck product reacting with the catalyst.
|
|
| 29. |
- Fridén, Mikael E, 1984-
(författare)
-
Development of Methods for Analysis of Valuable Compounds in By-products from Agricultural and Forestry Industrial Sectors
- 2015
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- A growing interest in sustainable development has made efficient utilisation of starting materials and, if they occur, by-products become increasingly important. Vast amounts of by-products are generated by the forestry and food industry. Incineration for energy production is one way to make use of these by-products but some of them contain compounds that would have an increased value if they were extracted, so called “high value species”. The by-products are often very complex, so reliable methods for analysis of the high value species are required in the development of processes to utilise them. A wide range of compounds can be analysed using chromatographic separation coupled to mass spectrometry, making it a powerful tool in the evaluation of methods for extracting high value species from industry by-products.This thesis is based on four studies of potential high value species. In the first study, methods were developed to differentiate isobaric flavonoids and then use this knowledge to determine the identity of the flavonoids in three different plant extracts. In the second study, three different methods to extract betulin from birch bark were evaluated regarding extracted amount and purity of betulin. One of the methods was then investigated in industrial scale using a model approach. In the third study, the flavonoid contents of lovage were determined and other major extracted compounds were investigated by high performance liquid chromatography coupled to electrospray ionisation mass spectrometry. Gas chromatography and supercritical fluid chromatography were used to obtain complementary information about major components. In the fourth study, high resolution mass spectrometry utilising two different types of fragmentation was used with the purpose of overcoming the shortcomings of the methods developed in the first study. The results indicated that it would be possible to develop methods compatible with chromatographic separation for differentiating different types of isobaric substituents. The ability of performing sequential fragmentation was used to investigate some isobaric aglycones by creating spectral trees, and unique pathways were found for each of them.
|
|
| 30. |
|
|
| 31. |
- Fridén, Mikael E, 1984-, et al.
(författare)
-
Evaluation and analysis of environmentally sustainable methodologies for extraction of betulin from birch bark with a focus on industrial feasibility
- 2016
-
Ingår i: Green Chemistry. - : Royal Society of Chemistry (RSC). - 1463-9262 .- 1463-9270. ; 18:2, s. 516-523
-
Tidskriftsartikel (refereegranskat)abstract
- Betulin from birch bark was extracted using two principally different extraction methodologies - classical Reflux Boiling (RB) and Pressurized Liquid Extraction (PLE). The extraction methods were analyzed based on both recovery and purity as well as for RB industrial feasibility. The purity and recovery for the different extraction methods were analyzed using High Performance Liquid Chromatography (HPLC) coupled with three different detection principles: Diode Array Detection (DAD), Mass Spectrometry (MS) and Charged Aerosol Detection (CAD). The chromatographic purity was determined by all detections whereas the DAD was used also for complementary gravimetric calculations of the purity of the extracts. The MS detection (in MS and MS/MS modes) was mainly used to characterize the impurities. Two steps to increase the purity of RB extracts were evaluated - pre-boiling the bark in water and precipitation by adding water to the extract. Finally, the methods were compared in terms of amounts of betulin produced and solvent consumed. The RB method including a precipitation step produced the highest purity of betulin. However, results indicate that PLE using three cycles with the precipitation step gives similar purities as for RB. The PLE method produced up to 1.6 times higher amount of extract compared to the RB method. However, the solvent consumption (liter solvent per gram product) for PLE was around 4.5 times higher as compared to the classical RB. PLE performed with only one extraction cycle gave results more similar to RB with 1.2 times higher yield and 1.4 times higher solvent consumption. The RB process was investigated on an industrial scale using a model approach and several important key-factors could be identified. The most energy demanding step was the recycling of extraction solvent which motivates that solvent consumption should be kept low and calculations show a great putative energy reduction by decreasing the ethanol concentration used in the RB process to lower than 90%.
|
|
| 32. |
- Fridén, Mikael E., et al.
(författare)
-
Strategies for differentiation of isobaric flavonoids using liquid chromatography coupled to electrospray ionization mass spectrometry
- 2014
-
Ingår i: Journal of Mass Spectrometry. - : Wiley. - 1076-5174 .- 1096-9888. ; 49:7, s. 646-663
-
Tidskriftsartikel (refereegranskat)abstract
- Flavonoids are a class of secondary plant metabolites existing in great variety in nature. Due to this variety, identification can be difficult, especially as overlapping compounds in both chromatographic separations and mass spectrometric detection are common. Methods for distinguishing isobaric flavonoids using MS2 and MS3 have been developed. Chromatographic separation of various plant extracts was done with RP-HPLC and detected with positive ESI-MS operated in information-dependent acquisition (IDA) mode. Two methods for the determination of flavonoid identity and substitution pattern, both featuring IDA criteria, were used together with the HPLC equipment. A third method where the collision energy was ramped utilized direct infusion. With the developed strategies, it is possible to differentiate between many isobaric flavonoids. Various classes of flavonoids were found in all of the plant extracts, in the red onion extract 45 components were detected and for 29 of them the aglycone was characterized, while the substituents were tentatively identified for 31 of them. For the strawberry extract, those numbers were 66, 30 and 60, and for the cherry extract 99, 56 and 71. The great variety of flavonoids, several of them isobaric, found in each of the extracts highlights the need for reliable methods for flavonoid characterization. Methods capable of differentiating between most of the isobars analyzed have been developed.
|
|
| 33. |
- Hawkes, Jeffrey A., et al.
(författare)
-
Complexity of dissolved organic matter in the molecular size dimension : insights from coupled size exclusion chromatography electrospray ionisation mass spectrometry
- 2019
-
Ingår i: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 218, s. 52-71
-
Tidskriftsartikel (refereegranskat)abstract
- This paper investigates the relationship between apparent size distribution and molecular complexity of dissolved organic matter from the natural environment. We used a high pressure size exclusion chromatography (HPSEC) method coupled to UV-Vis diode array detection (UV-DAD) and electrospray ionisation mass spectrometry (ESI-MS) in order to compare the apparent size of natural organic matter, determined by HPSEC-UV and the molecular mass determined online by ESI-MS. We found that there was a clear discrepancy between the two methods, and found evidence for an important pool of organic matter that has a strong UV absorbance and no ESI-MS signal. Contrary to some previous research, we found no evidence that apparently high molecular weight organic matter is constituted by aggregates of low molecular weight (<1000 Da) material. Furthermore, our results suggest that the majority of apparent size variability within the ESI ionisable pool of organic matter is due to secondary interaction and exclusion effects on the HPSEC column, and not true differences in hydrodynamic size or intermolecular aggregation.
|
|
| 34. |
- Hawkes, Jeffrey A., et al.
(författare)
-
Extreme isomeric complexity of dissolved organic matter found across aquatic environments
- 2018
-
Ingår i: Limnology and Oceanography Letters. - : Wiley. - 2378-2242. ; 3:2, s. 21-30
-
Tidskriftsartikel (refereegranskat)abstract
- The natural aquatic environment contains an enormous pool of dissolved reduced carbon, present as ultra‐complex mixtures that are constituted by an unknown number of compounds at vanishingly small concentrations. We attempted to separate individual structural isomers from several samples using online reversed‐phase chromatography with selected ion monitoring/tandem mass spectrometry, but found that isomeric complexity still presented a boundary to investigation even after chromatographic simplification of the samples. However, it was possible to determine that the structural complexity differed among samples. Our results also suggest that extreme structural complexity was a ubiquitous feature of dissolved organic matter (DOM) in all aquatic systems, meaning that this diversity may play similar roles for recalcitrance and degradation of DOM in all tested environments.
|
|
| 35. |
- Khangure, Simon R., et al.
(författare)
-
Carotid near-occlusion frequently has high peak systolic velocity on Doppler ultrasound
- 2018
-
Ingår i: Neuroradiology. - : Springer. - 0028-3940 .- 1432-1920. ; 60:1, s. 17-25
-
Tidskriftsartikel (refereegranskat)abstract
- Purpose: Carotid near-occlusion is a tight atherosclerotic stenosis of the internal carotid artery (ICA) resulting in decrease in diameter of the vessel lumen distal to the stenosis. Near-occlusions can be classified as with or without full collapse, and may have high peak systolic velocity (PSV) across the stenosis, mimicking conventional > 50% carotid artery stenosis. We aimed to determine how frequently near-occlusions have high PSV in the stenosis and determine how accurately carotid Doppler ultrasound can distinguish high-velocity near-occlusion from conventional stenosis.Methods: Included patients had near-occlusion or conventional stenosis with carotid ultrasound and CT angiogram (CTA) performed within 30 days of each other. CTA examinations were analyzed by two blinded expert readers. Velocities in the internal and common carotid arteries were recorded. Mean velocity, pulsatility index, and ratios were calculated, giving 12 Doppler parameters for analysis.Results: Of 136 patients, 82 had conventional stenosis and 54 had near-occlusion on CTA. Of near-occlusions, 40 (74%) had high PSV (≥ 125 cm/s) across the stenosis. Ten Doppler parameters significantly differed between conventional stenosis and high-velocity near-occlusion groups. However, no parameter was highly sensitive and specific to separate the groups.Conclusion: Near-occlusions frequently have high PSV across the stenosis, particularly those without full collapse. Carotid Doppler ultrasound does not seem able to distinguish conventional stenosis from high-velocity near-occlusion. These findings question the use of ultrasound alone for preoperative imaging evaluation.
|
|
| 36. |
- Lindahl, Sofia, et al.
(författare)
-
Exploring the possibility of using a thermostable mutant of β-glucosidase for rapid hydrolysis of quercetin glucosides in hot water
- 2010
-
Ingår i: Green Chemistry. - : The Royal Society of Chemistry. - 1463-9262 .- 1463-9270. ; 12:1, s. 159-168
-
Tidskriftsartikel (refereegranskat)abstract
- The antioxidant quercetin was extracted from yellow onion waste and converted to its aglycone form by a combination of subcritical water extraction and enzymatic hydrolysis. The hydrolytic step was catalysed by a double residue (N221S, P342L) mutant of the thermostable beta-glucosidase (TnBgl1A), isolated from the thermophile Thermotoga neapolitana and cloned and produced in E. coli. The activity of wt TnBgl1A was shown to be dependent on the position of the glucosylation on the quercetin backbone, favouring hydrolysis of quercetin-4'-glucoside over quercetin-3-glucoside. The mutated variant of the enzyme harboured a mutation in the +2 sub-site (N221S) and showed increased catalytic efficiency in quercetin-3-glucoside hydrolysis and also to a certain extent hydrolysis of quercetin-4'-glucoside. The mutated enzyme was used directly in yellow onion extracts, prepared by subcritical water extraction, resulting in complete hydrolysis of the glucosylated flavonoids quercetin-3,4'-diglucoside, quercetin-4'-glucoside, quercetin-3-glucoside, isorhamnetin-4'-glucoside and isorhamnetin-3,4'-diglucoside. To complete hydrolysis within five minutes, 3 mg of TnBgl1A_N221S was used per gramme of onion (dry weight). A life cycle assessment was done to compare the environmental impact of the new method with a conventional solid-liquid extraction-and-hydrolysis method utilising aqueous methanol and hydrochloric acid. Comparison of the methods showed that the new method is preferable regarding primary energy consumption and global warming potential. Another advantage of this method is that handling of toxic chemicals (methanol and HCl) is avoided. This shows that combined subcritical water extraction/enzyme hydrolysis is both a fast and sustainable method to obtain quercetin from onion waste.
|
|
| 37. |
|
|
| 38. |
- Lindh, Jonas, et al.
(författare)
-
Synthesis of styrenes by palladium(II)-catalyzed vinylation of arylboronic acids and aryltrifluoroborates by using vinyl acetate
- 2009
-
Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 15:18, s. 4630-4636
-
Tidskriftsartikel (refereegranskat)abstract
- Reactions of aromatic and heteroaromatic boronic acids or aryltrifluoroborate salts with vinyl acetate in the presence of a palladium(II) catalyst give the corresponding styrenes in good yields. This Heck reaction proceeds with microwave heating in less than 30 min at 140 degrees C in the absence of base and tolerates a variety of substituents. No palladium reoxidant is needed and the vinylation is performed under non-inert conditions. Mass spectrometry (electrospray ionization mass spectrometry (ESIMS) and tandem mass spectrometry (MS/MS)) was used to identify cationic palladium-containing complexes in ongoing reactions. The key intermediates that have been detected, together with experiments that used deuterated vinyl acetate, support the existence of catalytically active palladium hydride species, and that it is the arylation of ethylene, not vinyl acetate, which generates the styrene product. The mechanism of the reaction is discussed in terms of the palladium(II) intermediates mentioned above.
|
|
| 39. |
- Liu, Jiayin, et al.
(författare)
-
Pressurised hot water extraction in continuous flow mode for thermolabile compounds : extraction of polyphenols in red onions
- 2014
-
Ingår i: Analytical and Bioanalytical Chemistry. - : Springer Science and Business Media LLC. - 1618-2642 .- 1618-2650. ; 406:2, s. 441-445
-
Tidskriftsartikel (refereegranskat)abstract
- Extraction and analysis of labile compounds in complex sample matrices, such as plants, is often a big analytical challenge. In this work, the use of a "green and clean" pressurised hot water extraction (PHWE) approach performed in continuous flow mode is explored. Experimental data for extraction and degradation kinetics of selected compounds were utilised to develop a continuous flow extraction (CFE) method targeting thermolabile polyphenols in red onions, with detection by high-performance liquid chromatography (HPLC)-diode array detection (DAD)-mass spectrometry (MS). Water containing ethanol and formic acid was used as extraction solvent. Method performance was focused on extraction yield with minimal analyte degradation. By adjusting the flow rate of the extraction solvent, degradation effects were minimised, and complete extraction could be achieved within 60 min. The CFE extraction yields of the polyphenols investigated were 80-90 % of the theoretically calculated quantitative yields and were significantly higher than the yields obtained by conventional methanol extraction and static batch extraction (70-79 and 58-67% of the theoretical yields, respectively). The precision of the developed method was lower than 8 % expressed as relative standard deviation.
|
|
| 40. |
- Najafpour, Mohammad Mahdi, et al.
(författare)
-
Solution structure of a seven coordinated manganese(II) complex via electrospray ionization mass spectrometry
- 2010
-
Ingår i: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy. - : Elsevier BV. - 1386-1425 .- 1873-3557. ; 75:3, s. 1168-1170
-
Tidskriftsartikel (refereegranskat)abstract
- The mononuclear complex [Mn(tptz)(CH3COO)(OH2)2]NO3 (1) was investigated by electrospray ionization mass spectrometry in aqueous solution at pH 4.5. Electrospray ionization mass spectrometry shows that mononuclear and dinuclear manganese cationic species are present in solution, probably in equilibrium with neutral 1. An experiment showed that the most important reaction in the presence of oxone (2KHSO5·KHSO4·K2SO4) is decoordination.
|
|
| 41. |
|
|
| 42. |
- Paraskova, Julia V., et al.
(författare)
-
Extraction and quantification of phosphorus derived from DNA and lipids in environmental samples
- 2013
-
Ingår i: Talanta. - : Elsevier BV. - 0039-9140 .- 1873-3573. ; 115, s. 336-341
-
Tidskriftsartikel (refereegranskat)abstract
- Understanding the flux and turnover of phosphorus (P) in the environment is important due to the key role P plays in eutrophication and in the ambition to find cost-effective measures to mitigate it. Orthophosphate diesters, including DNA and phospholipids (PLs), represent a potentially degradable P pool that could support future primary production and eutrophication. In this study, extraction techniques were optimized and combined with colorimetric determination of extracted P to provide a selective quantification method for DNA-P and PL-P in agricultural soil, sediment and composted manure. The proposed method is rapid and reproducible with an RSD of <10%. Recovery, evaluated by spiking the sample matrices with DNA and PL standards, was over 95% for both DNA and PLs. The method can be used for the determination of the pool size of the two organic P fractions. Results show that DNA-P comprises 3.0% by weight of the total P (TP) content in the studied soil, 10.4% in the sediment and 8.4% in the compost samples. The values for PL-P are 0.5%, 6.0% and 1.7% for soil, sediment and compost, respectively.
|
|
| 43. |
|
|
| 44. |
- Paraskova, Julia V.
(författare)
-
Organic phosphorus speciation in environmental samples : Method development and applications
- 2014
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis investigates the development of new methodology for the identification and quantification of organic phosphorus compounds in environmental samples.Phosphorus is a vital element for primary production and one of the factors contributing to eutrophication. Eutrophication of aquatic systems leads to algal blooms, changes in ecological balance and deteriorating water quality. Difficulties in studying organic phosphorus stem from the fact that organic phosphorus is present in the environment in a variety of forms and each form may have different degradation and turnover time, having very different effects on eutrophication.New methods for the quantification of phosphorus derived from three groups of organic phosphorus compounds were developed. For the determination of phosphorus derived from DNA and phospholipids selective extraction was combined with digestion and colorimetric determination of the extracted phosphate. For quantification of inositol phosphates high performance liquid chromatography was coupled with tandem mass spectrometry using electrospray ionization. The methods were applied to studying the distribution of these compounds in a small catchment and in the case of DNA-P and phospholipid-P, the degradation of the fractions in lake sediments. The studies showed that phosphorus bound to DNA, phospholipids and inositol phosphates constitute a sizeable part of the total phosphorus in different environmental samples. The phospholipid-P fraction was the smallest one, accounting for, on average, only a few percent of the total phosphorus in the sample. Inositol phosphates were most prevalent in the soils, with inositol hexakisphosphate accounting for over 10% of the total phosphorus content. The highest content of DNA-P was found in sediments and it was shown that DNA-P degrades more rapidly than phospholipid-P and therefore plays a more critical role in internal loading.
|
|
| 45. |
|
|
| 46. |
- Paraskova, Julia V., et al.
(författare)
-
Speciation of Inositol Phosphates in Lake Sediments by Ion-Exchange Chromatography Coupled with Mass Spectrometry, Inductively Coupled Plasma Atomic Emission Spectroscopy, and P-31 NMR Spectroscopy
- 2015
-
Ingår i: Analytical Chemistry. - : American Chemical Society (ACS). - 0003-2700 .- 1520-6882. ; 87:5, s. 2672-2677
-
Tidskriftsartikel (refereegranskat)abstract
- A method for the detection and speciation of inositol phosphates (InsP(n)) in sediment samples was tested, utilizing oxalateoxalic acid extraction followed by determination by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLCMS/MS) using electrospray ionization (ESI) in negative mode. The chromatographic separation was carried out using water and ammonium bicarbonate as mobile phase in gradient mode. Data acquisition under MS/MS was attained by multiple reaction monitoring. The technique provided a sensitive and selective detection of InsP(n) in sediment samples. Several forms of InsPn in the oxalateoxalic acid extracted sediment were identified. InsP(6) was the dominating form constituting 0.250 mg P/g DW (dry weight); InsP(5) and InsP(4) constituted 0.045 and 0.014 mg P/g DW, respectively. The detection limit of the LCESI-MS/MS method was 0.03 mu M InsPn, which is superior to the currently used method for the identification of InsPn, P-31 nuclear magnetic resonance spectroscopy (P-31 NMR). Additionally sample handling time was significantly reduced.
|
|
| 47. |
- Paraskova, Julia V., et al.
(författare)
-
Turnover of DNA-P and phospholipid-P in lake sediments
- 2014
-
Ingår i: Biogeochemistry. - : Springer Science and Business Media LLC. - 0168-2563 .- 1573-515X. ; 119:1-3, s. 361-370
-
Tidskriftsartikel (refereegranskat)abstract
- Identifying and quantifying the forms of phosphorus (P) in lake sediments is a prerequisite for understanding lake trophic status and possible exports of P downstream. Organic P is one of the most important P forms found in the sediment, where orthophosphate diesters, including DNA and phospholipids, represent a degradable P pool that can support primary production and eutrophication. In this study, sediment cores from the eutrophic Lake Erken and the oligotrophic Lake Ånnsjön, both in steady state regarding long-term P input revealed trends in the degradation of DNA-P and PL-P with sediment depth. Comparisons were performed based on the differentiation of essentially permanent or recalcitrant P and temporary, potentially mobile P for the respective fractions. The temporary P pool was defined as the part of the total P pool calculated for values higher than the level at which the measured P concentration converged to a constant value and the recalcitrant pool was defined as the difference between the total and the temporary. The temporary diester-P pool comprised over 20 % of the total temporary P in Lake Erken and around 4 % in Lake Ånnsjön. The decrease in P concentrations with depth was more rapid for DNA-P compared to PL-P in both lakes, suggesting that DNA-P has a more prominent role in internal loading. The study shows that P mobilization potential can be different for different P fractions, which is important when assessing their contribution to internal loading of P within an aquatic system.
|
|
| 48. |
- Patriarca, Claudia, et al.
(författare)
-
Character and environmental lability of cyanobacteria-derived dissolved organic matter
- 2021
-
Ingår i: Limnology and Oceanography. - : Wiley. - 0024-3590 .- 1939-5590. ; 66:2, s. 496-509
-
Tidskriftsartikel (refereegranskat)abstract
- Autotrophic dissolved organic matter (DOM) is central to the carbon biogeochemistry of aquatic systems, and the full complexity of autotrophic DOM has not been extensively studied, particularly by high-resolution mass spectrometry (HRMS). Terrestrial DOM tends to dominate HRMS studies in freshwaters due to the propensity of such compounds to ionize by negative mode electrospray, and possibly also because ionizable DOM produced by autotrophy is decreased to low steady-state concentrations by heterotrophic bacteria. In this study, we investigated the character of DOM produced by the widespread cyanobacteria Microcystis aeruginosa using high-pressure liquid chromatography—electrospray ionization—high-resolution mass spectrometry. M. aeruginosa produced thousands of detectable compounds in axenic culture. These compounds were chromatographically resolved and the majority were assigned to aliphatic formulas with a broad polarity range. We found that the DOM produced by M. aeruginosa was highly susceptible to removal by heterotrophic freshwater bacteria, supporting the hypothesis that this autotroph-derived organic material is highly labile and accordingly only seen at low concentrations in natural settings.
|
|
| 49. |
- Patriarca, Claudia, 1986-
(författare)
-
Characterisation of natural dissolved organic matter with liquid chromatography and high resolution mass spectrometry
- 2020
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Dissolved organic matter (DOM) is one of the most heterogeneous and complex mixture on Earth. DOM plays a crucial role in biogeochemical processes on the global scale and it is essential to sustain and regulate the biological processes in aquatic ecosystems. DOM originates from a multitude of biological, physical and chemical transformations, leading to its phenomenal chemical diversity. In order to understand and predict its effect on the global carbon cycle, an intimate characterization at molecular level is necessary. The investigation of the extraordinary complexity of the DOM mixture represents a compelling challenge for analytical chemistry. The focus of this thesis was the development of methods for the characterization of DOM in natural waters. High resolution mass spectrometry (HRMS), was combined with high pressure liquid chromatography (HPLC) and electrospray ionization (ESI), to investigate the chemical diversity of DOM. The first study demonstrated that cutting-edge techniques (such as the Fourier-transform ion cyclotron resonance mass spectrometer - FTICR-MS), are not indispensable to disclose essential information on the DOM molecular composition, in fact the Orbitrap mass analyser is a suitable alternative for the analysis of complex natural mixtures. In the second study, the potential benefits offered by the online coupling of HPLC and HRMS instruments were explored, revealing significant advantages in terms of analysis time, achievable information and versatility of the method. The advantages of online separation were further confirmed in the third study, focused on the characterization of autochthonous labile DOM. Chromatographically resolved profiles emerged from the bulk-DOM, allowing the monitoring of labile autochthonous components in presence of heterotrophic bacteria. Despite the advantages achieved by the application of online separation, a strong limiting factor in DOM characterization is the ESI source, suitable only for the analysis of the DOM fraction susceptible to ionization. In the last study, the extent of the DOM material prone to ionization was estimated, revealing the occurrence of an extensive portion of the material resistant to routinely employed ESI approach. The full characterization of DOM is still an open challenge and the combination of multiple techniques is fundamental to unravel is extreme intricacy.
|
|
| 50. |
- Petersson, Erik V., et al.
(författare)
-
Pressurized Hot Water Extraction of anthocyanins from red onion : A study on extraction and degradation rates
- 2010
-
Ingår i: Analytica Chimica Acta. - : Elsevier BV. - 0003-2670 .- 1873-4324. ; 663:1, s. 27-32
-
Tidskriftsartikel (refereegranskat)abstract
- Pressurized Hot Water Extraction (PHWE) is a quick, efficient and environmentally friendly technique for extractions. However, when using PHWE to extract thermally unstable analytes, extraction and degradation effects occur at the same time, and thereby compete. At first, the extraction effect dominates, but degradation effects soon take over. In this paper, extraction and degradation rates of anthocyanins from red onion were studied with experiments in a static batch reactor at 110 °C. A total extraction curve was calculated with data from the actual extraction and degradation curves, showing that more anthocyanins, 21–36% depending on the species, could be extracted if no degradation occurred, but then longer extraction times would be required than those needed to reach the peak level in the apparent extraction curves. The results give information about the different kinetic processes competing during an extraction procedure.
|
|
