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- Alimohammadzadeh, Rana
(författare)
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Eco-friendly and Catalytic Surface Engineering of Cellulose and Nanocellulose
- 2021
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The non-stop use of petroleum-based materials such as plastics can generate significant environmental problems, including pollution of the oceans and increased CO2 levels, and cause diseases like cancer due to the starting monomers. Consequently, increased use of sustainable and non-toxic polymers and monomers is required to address these issues. Cellulose, generously supplied by Mother Nature, is the most abundant biopolymer on Earth. Nanocellulose is a sustainable polymer extracted from the cellulose inwood or produced by bacteria and algae. This biodegradable nanomaterialhas recently been receiving intense research attention, since it has great potential for use in a broad range of industrial and biomedical applications. However, it has limitations such as moisture sensitivity and incompatibility with hydrophobic materials due to its hydrophilic nature. Chemical modification is necessary for it to fulfill the requirements for applications that require high moisture resistance and water repellency. Unfortunately, several of the existing methods involve harsh and toxic conditions or reagents. In this thesis, together with my co-workers, I have employed the toolbox of organocatalysis for accomplishing eco-friendly and innovative surface modification of cellulose and nanocellulose. The organocatalysts we usedmost in our research are the naturally abundant and industrially relevantorganic acids tartaric acid and citric acid.Direct catalytic esterification of cellulose nanocrystal (CNC) with thioglycolicacid was performed either in suspension or on solid surfaces such as films and foams. We found that the reaction was accelerated by tartaric acid but could also be autocatalytic with respect to the thioglycolic acid under certain conditions. The synthesized CNC-SH was further exploited as a heterogeneous reducing agent as well as a handle for further nanocellulose modifications. This was demonstrated by using CNC-SH as a heterogenous reducing agent of Cu(II) to Cu(I), which is essential for allowing the Cu to actas a catalyst for 2,3-dipolar cycloaddition reactions between azides andalkynes. We also showed that the thia-modified CNC could undergo further functionalizing via thiol-ene click chemistry reactions, for example, we attached fluorescent compounds such as TAMRA and quinidine.Herein we provide a fluorine-free method to prepare superhydrophobic CNC film with excellent water-resistance properties by combining self-assemblyand organocatalysis. Self-assembly of CNC via vacuum filtration resulted in xa film with a specific roughness at the microscale. Next, the catalytic silylation with a variety of alkoxysilanes in the presence of natural organic acids such as tartaric acid and citric acid was performed. The successful implementation of our method resulted in a super-hydrophobic CNC film (water contact angleover 150°) with excellent water-resistance. Thus, the combination of the selfassembly of a rough surface with catalytic surface modification resulted in a phenomenon like the “lotus effect” as exhibited by the leaves of the lotus flower. An investigation of the oxygen permeability of the octadecyltrimethoxysilane-modified CNC film revealed that it significantly decreased at high relative humidity compared with unmodified CNC films.In this thesis, the fabrication of hydrophobic and functionalized MTM/CNF nanocomposites using organocatalytic surface modification with a large variety of alkoxysilanes is also performed. The surface modifications are mildand the mechanical strength of the Nacre-mimetic nanocomposites is preserved. Elemental mapping analysis revealed that the silane modification occurred predominantly on the surface.A combination of organocatalyst and biopolyelectrolyte complex was appliedfor surface engineering of chemi-thermomechanical pulp (CTMP) and bleached sulfite pulp (BSP). The reaction was performed using a synergistic combination of an organocatalyst with a polyelectrolyte (PE) complex. Using this method, the strength properties of CTMP and BSP sheets were significantly increased (up to 100% in Z-strength for CTMP). Further investigations of the distribution of the PE complex were then performed using TAMRA and quinidine labeling and confocal laser scanningmicroscopy. This revealed that an even distribution of the cationic starch component of the PE complex had occurred within the CTMP-based paper sheets, which follows its lignin distribution pattern.
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| 2. |
- Essén, Sofia
(författare)
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Hydroxamate Siderophores and Low Molecular Mass Organic Acids in Terrestrial and Aquatic Environments Determined by Liquid Chromatography Mass Spectrometry
- 2007
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Siderophores are low molecular mass organic compounds with high iron(III) stability constants. They are produced by many microorganisms, often in combination with low molecular mass organic acids (LMMOAs). Both siderophores and LMMOAs accelerate mineral weathering, thereby enhancing mineral nutrient availability. Siderophore concentrations in natural environments, however, are largely unknown. In the present work, analytical methods based on liquid chromatography (LC) electrospray ionization mass spectrometry (ESI‐MS) were developed and used for concentration determination of selected hydroxamate siderophores and LMMOAs. The use of capillary LC with on‐line pre‐concentration via column switching enabled siderophore quantification with detection limits of 0.1 ‐ 5 nM. Through solid phase extraction even lower detection limits were achieved. In Swedish podzol soil solutions concentrations up to 12 nM ferricrocin and 2 nM ferrichrome were found in the upper soil layes. Additionally, in axenic pine (Pinus sylvestris) seedling cultures, the ectomycorrhizal fungus Hebeloma crustuliniforme was shown to produce ferricrocin as the main siderophore. Moreover, ferricrocin was found in enriched Baltic Sea cyanobacterial populations at concentrations up to 1 nM, while concentrations up to 0.05 nM ferrioxamine B were determined in Baltic Sea surface waters during cyanobacterial blooms. Siderophores have strong affinities for some actinides and may affect radionuclide mobilization in deep subsurface nuclear wase repositories. Two subsurface bacterial strains were shown to produce siderophores under aerobic conditions, i.e. Pseudomonas stutzeri produced mainly ferrioxamine E and Pseudomonas fluorescens produced one pyoverdin siderophore. Siderophores produced by aerobically grown P. stutzeri were not observed either in anaerobic cultures or in deep subsurface water samples.
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| 3. |
- Fredriksson, Mattias
(författare)
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Efficient algorithms for highly automated evaluation of liquid chromatography - mass spectrometry data
- 2010
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Liquid chromatography coupled to mass spectrometry (LC‐MS) has due to its superiorresolving capabilities become one of the most common analytical instruments fordetermining the constituents in an unknown sample. Each type of sample requires a specificset‐up of the instrument parameters, a procedure referred to as method development.During the requisite experiments, a huge amount of data is acquired which often need to bescrutinised in several different ways. This thesis elucidates data processing methods forhandling this type of data in an automated fashion.The properties of different commonly used digital filters were compared for LC‐MS datade‐noising, of which one was later selected as an essential data processing step during adeveloped peak detection step. Reconstructed data was further discriminated into clusterswith equal retention times into components by an adopted method. This enabled anunsupervised and accurate comparison and matching routine by which components fromthe same sample could be tracked during different chromatographic conditions.The results show that the characteristics of the noise have an impact on the performanceof the tested digital filters. Peak detection with the proposed method was robust to thetested noise and baseline variations but functioned optimally when the analytical peaks hada frequency band different from the uninformative parts of the signal. The algorithm couldeasily be tuned to handle adjacent peaks with lower resolution. It was possible to assignpeaks into components without typical rotational and intensity ambiguities associated tocommon curve resolution methods, which are an alternative approach. The underlyingfunctions for matching components between different experiments yielded satisfactoryresults. The methods have been tested on various experimental data with a high successrate.
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| 4. |
- Norström, Sara H
(författare)
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Soil and stream water chemistry in a boreal catchment - interactions, influences of dissolved organic matter and effects of wood ash application
- 2010
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Two small bordering catchments in Bispgården, Central Sweden, wereinvestigated in regard to soil solution and stream water chemistry during the frostfree seasons of 2003-2007. Both catchments were drained by first order streams,Fanbergsbäcken and Gråbergsbäcken, and in Fanbergsbäckens catchment anextensive investigation of the soil and soil solution chemistry was conducted bylysimeter and centrifugation sampling. The area of intensive soil solutioninvestigation was situated in a slope towards a stream incorporating a rechargearea, with podzolic soil, and a discharge area close to the stream with an arenosolsoil. Samples were continuously taken in both the recharge- and the discharge areaof the slope, and stream water was sampled in the streams of both catchments. Themain variables of interest of the study were the interactions, the influence ofdissolved organic carbon and the effects of wood ash application to soil solutionand stream water.The natural variations and the interactions between soil solution and streamwater were monitored during 2003-2004. In soil solution, most of the investigatedsubstances tended to increase during the growing season, due to weathering andmicrobial degradation of biota. Ca, Mg, Al and Fe were highly associated todissolved organic carbon (DOC) throughout the catchment. The low molecularfraction of DOC seemed to have a higher impact on the soil processes in therecharge area, while high molecular DOC was more important for transport ofcations in the discharge area and the stream water.The concentration of different substances in the two streams differedsignificantly, even though the catchments were similar in size, shape andforestation. The seasonal patterns of most of the substances measured weresignificantly correlated between the streams, however. Cations and pH correlatedwell with DOC and flow. The flow pattern driven by precipitation seems to be thedriver of the stream water chemistry.Wood ash was applied at a dosage of 3 ton/ha to one of the catchments in theautumn of 2004, to investigate the initial effects on the soil solution- and streamwater chemistry. WAA is recommended by the Swedish Forest Agency tocounteract acidification in soil and runoff that may be caused by an intensivebiomass harvesting. The impact of the WAA was studied during 2005-2006.Compared to the control temporarily higher concentrations of K, Ca and SO4 wereobserved in the soil solution of the ashed area. In the stream water the effects of theWAA were easier to distinguish due to higher sampling frequency. The strongesteffect was seen for K, but increases in the stream water were also noted for DOC,Ca, Mg, Si, Cl and malonate. No increase in pH could be statistically verifiedhowever, and overall the initial effects of the WAA seem mild.
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| 6. |
- Vilches, Ana Paola
(författare)
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Effects of Bio-Ash Amendments on the Metabolism of Ectomycorrhizal Fungi : A Method Development and Metabolomic Study
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Forest ecosystems have played a fundamental role in the development of our society. Since the beginning of the civilization, forest have provided us with wood as a product for construction, tools, furniture and domestic heating. The well-being of the forest is therefore fundamental to our existence. Today, our growing societies have increased energy needs; the resulting depletion of fossil reserves and the effects of their use has again shown how the forest is among the most important alternatives for sustainability of our ecosystem. In order to responsibly make this resource a key part of our energy and material supply, we need to understand how forestry practices influence the different processes taking place in the forest ecosystems.The use of raw material from forest as energy source produces huge amounts of ash. The ash contains the base cations that have once been translocated from soil to the upper parts of the trees. Ash recycling has therefore been suggested as a measure to counteract soil acidification due to extensive harvest. Since spreading of ash can have great effects on the forest, it is important to understand which these effects are and how big they might be.This thesis focuses on the effects that such an ash recycling may have on the metabolism of ectomycorrhizal fungi; that is, fungi that are able to colonize root of trees, and contribute to the acquisition of nutrients and water from soil. The work presented here utilized an in vitro metabolomic approach on eight species of ectomycorrhizal fungi normally found in boreal forests. A targeted metabolomic study addressed the effects of ash amendments on growth, external pH and the exudation of low molecular mass organic acids, amino acids and hydroxamate siderophores. This was complemented by an untargeted metabolomic study to address the effects of ash amendment on the general metabolism of the fungal species.Analyses were performed with well-established chemical methods, and some that had to be developed specifically for this thesis work. A method for the analysis of amino acids without derivatization and yet compatible with mass spectrometry had to be developed and validated. The result was a robust method that works well with external calibration, shows good long-term stability, relatively low detections limits and high sample throughput. A screening protocol for the determination of siderophores from mass spectrometry data was also established.The metabolomic studies showed that bio-ash amendment increased the exudation of low molecular mass organic compounds from all the studied species. This means that the species tended to exude more of the same compounds compared to the controls without ash. In some cases, the bio-ash also triggered the exudation of new compounds. There was some exceptions, though; bio-ash amendment had negative effects on the exudation of certain metabolites, but these negative effects were of lower magnitude compared to the positive effects.Both metabolomics studies showed a differentiation between the ascomycetes and the basidiomycetes species. The targeted metabolomic study, indicated a trade-off in the utilization of carbon for accumulation of biomass or for the exudation of low molecular mass organic compounds, in which the ascomycetes accumulated more carbon as biomass compared to the basidiomycetes. According to the untargeted metabolomic study, the ascomycetes species presented the greatest number of metabolites that were influenced significantly by ash treatment, either as increase or decrease.Adding extracted ash to the culturing medium at the beginning of the experiment increased the pH, but this was counteracted by species metabolism as exudation of organic acids correlated with a drop in external pH. Ash treatment triggered the total exudation of low molecular mass organic acids in five of the eight studied species and especially in Cortinarius glaucopus. Ash treatment also triggered the exudation of amino acids from Tomentellopsis submollis and ferricrocin from Hymenoscyphus ericae.Of note was that no metabolite significantly influenced by ash was found to be common to all species, indicating that the ash amendments mainly affected the secondary metabolism under the culturing conditions used. Additionally, the ascomycetes Hymenoscyphus ericae exuded the greatest number of metabolites affected by ash that were exuded only by a single species. Conversely, Piloderma olivaceum exuded the largest number of unique metabolites not influenced by ash.
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