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  • 1.
    Aguilar, Ximena
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Weise, Christoph
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Wolf-Watz, Magnus
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Wittung-Stafshede, Pernilla
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Macromolecular crowding extended to a heptameric system: the co-chaperonin protein 102011In: Biochemistry, ISSN 0006-2960, E-ISSN 1520-4995, Vol. 50, no 14, p. 3034-3044Article in journal (Refereed)
    Abstract [en]

    Experiments on monomeric proteins have shown that macromolecular crowding can stabilize toward heat perturbation and also modulate native-state structure. To assess the effects of macromolecular crowding on unfolding of an oligomeric protein, we here tested the effects of the synthetic crowding agent Ficoll 70 on human cpn10 (GroES in E. coli), a heptameric protein consisting of seven identical β-barrel subunits assembling into a ring. Using far-UV circular dichroism (CD), tyrosine fluorescence, nuclear magnetic resonance (NMR), and cross-linking experiments, we investigated thermal and chemical stability, as well as the heptamer-monomer dissociation constant, without and with crowding agent. We find that crowding shifts the heptamer-monomer equilibrium constant in the direction of the heptamer. The cpn10 heptamer is both thermally and thermodynamically stabilized in 300 mg/mL Ficoll 70 as compared to regular buffer conditions. Kinetic unfolding experiments show that the increased stability in crowded conditions, in part, is explained by slower unfolding rates. A thermodynamic cycle reveals that in presence of 300 mg/mL Ficoll the thermodynamic stability of each cpn10 monomer increases by over 30%, whereas the interfaces are stabilized by less than 10%. We also introduce a new approach to analyze the spectroscopic data that makes use of multiple wavelengths: this provides robust error estimates of thermodynamic parameters.

  • 2. Borgström, Johan
    et al.
    Egermayer, Monica
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Chemistry.
    Quist, Per-Ola
    Piculell, Lennart
    Liquid crystallinity versus gelation of kappa-carrageenan in mixed salts: effects of molecular weight, salt composition, and ionic strength1998In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 14, no 17, p. 4935-44Article in journal (Refereed)
    Abstract [en]

    The recently discovered isotropic/nematic phase transition in kappa-carrageenan was further examined by macroscopic observations and by NMR. A state diagram, which is the equivalent of a phase diagram but including also nonequilibrium states (in our case a gel), was established in the mixed salt solutions of NaI/CsI where the competition between phase separation and gelation could be studied. The phase boundaries of the nematic phase depended on molecular weight and ionic strength qualitatively as expected for a charged rigid polymer. From these data the persistence length of the kappa-carrageenan helix was estimated as 60-90 nm. The volume fraction of the nematic phase depended sensitively on the overall helical content. In coexisting phases, the helical content was larger in the nematic than in the isotropic phase.

  • 3.
    Bui, Nhat Thi Hong
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Jiang, Wen
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Irgum, Knut
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Synthesis of poly(N-[tris(hydroxymethyl)methyl]acrylamide) functionalized porous silica for application in hydrophilic interaction chromatography2012In: Journal of Separation Science, ISSN 1615-9306, E-ISSN 1615-9314, Vol. 35, no 23, p. 3257-3269Article in journal (Refereed)
    Abstract [en]

    Porous silica coated by a highly hydrophilic and nonionic tentacle-type polymeric layer was synthesized by free radical "grafting from" polymerization of N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]-2-propenamide (TRIS-acrylamide) in partly aqueous solutions. The radical initiator sites were incorporated on the silica surfaces via a two-step reaction comprising thionyl chloride activation and subsequent reaction with tert-butyl hydroperoxide. The surface-bound tert-butylperoxy groups were then used as thermally triggered initiators for graft polymerization of TRIS-acrylamide. The synthesized materials were characterized by diffusive reflectance Fourier transform infrared specotroscopy, X-ray photoelectron spectroscopy, and CHN elemental analysis. Photon correlation spectroscopy was used to determine changes in ζ-potentials resulting from grafting, (29) Si magic angle spinning nuclear magnetic resonance spectroscopy (MAS-NMR) spectroscopy was used to assess the ratio of silanol to siloxane groups in the substrate and the grafted material, and the changes in surface area and mesopore distribution were determined by nitrogen cryosorption. Chromatographic evaluation in hydrophilic interaction chromatography (HILIC) mode showed that the materials were suitable for use as stationary phases, featuring good separation efficiency, a comparatively high retention, and a selectivity that differed from most commercially available HILIC phases. A comparison of this neutral phase with a previously reported N-(2-hydroxypropyl)-linked TRIS-type hydrophilic tentacle phase with weak anion exchange functionality revealed substantial differences in retention patterns.

  • 4.
    Dingeldein, Artur P. G.
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Lidman, Martin
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Gröbner, Gerhard
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Dynamical and Structural Alterations withing Lipid-Protein Assemblies Control Apoptotic Pore Formation - A Solid State NMR Study2016In: Biophysical Journal, ISSN 0006-3495, E-ISSN 1542-0086, Vol. 110, no 3, p. 59A-60AArticle in journal (Other academic)
  • 5.
    Dingeldein, Artur Peter Günther
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Pokorna, Sarka
    Lidman, Martin
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sachl, Radek
    Hof, Martin
    Gröbner, Gerhard
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Apoptotic Bax at Oxidatively Stressed Mitochondrial Membranes: Lipid Dynamics and Permeabilization2017In: Biophysical Journal, ISSN 0006-3495, E-ISSN 1542-0086, Vol. 112, no 10, p. 2147-2158Article in journal (Refereed)
    Abstract [en]

    Mitochondria are crucial compartments of eukaryotic cells because they function as the cellular power plant and play a central role in the early stages of programmed cell death (apoptosis). To avoid undesired cell death, this apoptotic pathway is tightly regulated by members of the Bcl-2 protein family, which interact on the external surface of the mitochondria, i.e., the mitochondrial outer membrane (MOM), and modulate its permeability to apoptotic factors, controlling their release into the cytosol. A growing body of evidence suggests that the MOM lipids play active roles in this permeabilization process. In particular, oxidized phospholipids (OxPls) formed under intracellular stress seem to directly induce apoptotic activity at the MOM. Here we show that the process of MOM pore formation is sensitive to the type of OxPls species that are generated. We created MOM-mimicking liposome systems, which resemble the cellular situation before apoptosis and upon triggering of oxidative stress conditions. These vesicles were studied using P-31 solid-state magic-angle-spinning nuclear magnetic resonance spectroscopy and differential scanning calorimetry, together with dye leakage assays. Direct polarization and cross-polarization nuclear magnetic resonance experiments enabled us to probe the heterogeneity of these membranes and their associated molecular dynamics. The addition of apoptotic Bax protein to OxPls-containing vesicles drastically changed the membranes' dynamic behavior, almost completely negating the previously observed effect of temperature on the lipids' molecular dynamics and inducing an ordering effect that led to more cooperative membrane melting. Our results support the hypothesis that the mitochondrion-specific lipid cardiolipin functions as a first contact site for Bax during its translocation to the MOM in the onset of apoptosis. In addition, dye leakage assays revealed that different OxPls species in the MOM-mimicking vesicles can have opposing effects on Bax pore formation.

  • 6.
    Driver, Gordon W.
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Huang, Yang
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Laaksonen, Aatto
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Wang, Yonglei
    Westlund, Per-Olof
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Correlated/non-correlated ion dynamics of charge-neutral ion couples: the origin of ionicity in ionic liquids2017In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 19, no 7, p. 4975-4988Article in journal (Refereed)
    Abstract [en]

    Proton/Fluoride spin-lattice ($T_1$) nuclear magnetic relaxation dispersion (NMRD) measurements of 1-butyl-3-methyl-$1H$-imidazolium hexa-fluorophosphate, [$C_4mim][PF_6]$, have been carried out using high field spectrometers and fast-field-cycling instrument at proton Larmor frequencies ranging from 10kHz to 40 MHz, at different temperatures. The NMRD profiles are interpreted by means of a simple relaxation model based on the inter- and intra-ionic dipole-dipole relaxation mechanism. Using an atomic molecular-ion dynamic simulation at 323 K the relevant spin dipole-dipole(DD) correlation functions are calculated. The results indicate the NMRD profiles can be rationalized using intra- and inter-ionic spin DD interactions, however, both are mainly modulated by ionic reorientation because of temporary correlations with cations, where modulation by translational diffusion plays a minor role. Reorientational dynamics of charge-neutral ion couples (i.e. $[C_4mim]^{...}[PF_6]$) and $[C_4mim]^{+}$ ions are in the nano-second (ns) time range whereas the reorientation of $[PF_6]{^-}$ is characterized by a reorientational correlation time in the pico-second (ps) regime. Based on the NMRD profiles we conclude the main relaxation mechanism for $[PF_6]{^-}$ is, due to fast internal reorientational motion, a partially averaged F-F intra and a F-H inter-ionic DD coupling as the anion resides in close proximity to its temporary oppositely charged cation partner. The F-$T_1$- NMRD data display a ns dispersions which is interpreted as being due to correlated reorientational modulations resultant from H-containing charge-neutral ion couple $[C_4mim]^{...}[PF_6]$. The analysis of ionicity is based on the free anion fraction, $f$ and it increase with temperature with $f$ $\rightarrow$ 1 at the highest temperatures investigated. The fraction is obtained from the H-F NMRD profiles as correlated-non-correlated dynamics of the ions. The analysis of $T_1$ relaxation rates of C, H, F and P at high fields cannot generally give the fraction of ion but are consistent with the interpretation based on the NMRD profiles with relaxation contributions due to DD-intra and -inter, CSA-intra (and -inter for C), including spin rotation for P. The investigation has led to a description of the mechanics governing ion transport in the title ionic liquid via identification of transient correlated/non-correlated ion dynamics.

  • 7. Drotz, Stina Harrysson
    et al.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Nilsson, Mats B
    Schleucher, Jürgen
    Umeå University, Faculty of Medicine, Department of Medical Biochemistry and Biophysics.
    Öquist, Mats G
    Both catabolic and anabolic heterotrophic microbial activity proceed in frozen soils2010In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 107, no 49, p. 21046-21051Article in journal (Refereed)
    Abstract [en]

    A large proportion of the global soil carbon pool is stored in soils of high-latitude ecosystems in which microbial processes and production of greenhouse gases proceed during the winter months. It has been suggested that microorganisms have limited ability to sequester substrates at temperatures around and below 0 °C and that a metabolic shift to dominance of catabolic processes occurs around these temperatures. However, there are contrary indications that anabolic processes can proceed, because microbial growth has been observed at far lower temperatures. Therefore, we investigated the utilization of the microbial substrate under unfrozen and frozen conditions in a boreal forest soil across a temperature range from -9 °C to +9 °C, by using gas chromatography-isotopic ratio mass spectrometry and (13)C magic-angle spinning NMR spectroscopy to determine microbial turnover and incorporation of (13)C-labeled glucose. Our results conclusively demonstrate that the soil microorganisms maintain both catabolic (CO(2) production) and anabolic (biomass synthesis) processes under frozen conditions and that no significant differences in carbon allocation from [(13)C]glucose into [(13)C]CO(2) and cell organic (13)C-compounds occurred between +9 °C and -4 °C. The only significant metabolic changes detected were increased fluidity of the cell membranes synthesized at frozen conditions and increased production of glycerol in the frozen samples. The finding that the processes in frozen soil are similar to those in unfrozen soil has important implications for our general understanding and conceptualization of soil carbon dynamics in high-latitude ecosystems.

  • 8.
    Drotz, Stina Harrysson
    et al.
    Department of Forest Ecology & Management, Swedish University of Agricultural Sciences. Umeå.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Schleucher, Jürgen
    Umeå University, Faculty of Medicine, Department of Medical Biochemistry and Biophysics.
    Nilsson, Mats
    Department of Forest Ecology & Management, Swedish University of Agricultural Sciences. Umeå.
    Öquist, Mats G
    Department of Forest Ecology & Management, Swedish University of Agricultural Sciences. Umeå.
    Effects of soil organic matter composition on unfrozen water content and heterotrophic CO2 production of frozen soils2010In: Geochimica et Cosmochimica Acta, ISSN 0016-7037, E-ISSN 1872-9533, Vol. 74, no 8, p. 2281-90Article in journal (Refereed)
    Abstract [en]

    Several recent studies have highlighted the importance of soil organic matter (SOM) mineralization at high latitudes during winter for ecosystem carbon (C) balances, and the ability of the soil to retain unfrozen water at sub-zero temperatures has been shown to be a major determinant of C mineralization rates. Further, SOM is believed to strongly influence the liquid water contents in frozen surface layers of boreal forest soils and tundra, but the mechanisms and specific factors involved are currently unknown. Here we evaluate the effects of the chemical composition of SUM on the amount of unfrozen water, the pore size equivalents in which unfrozen water can exist, and the microbial heterotrophic activity at sub-zero temperatures in boreal forest soils. To do this, we have characterized the chemical composition of SUM in forest soil samples (surface O-horizons) using solid state CP-MAS (cross polarization magic angle spinning) NMR spectroscopy. The acquired information was then used to elucidate the extent to which different fractions of SUM can explain the observed variations in unfrozen water content, pore size equivalents, and biogenic CO2 production rates in the examined soil samples under frozen conditions (-4 degrees C). The data evaluation was done by the use of principal component analysis (PCA) and projections to latent structures by means of partial least square (PLS). We conclude that aromatic, O-aromatic, methoxy/N-alkyl and alkyl C are the major SOM components affecting frozen boreal forest soil's ability to retain unfrozen water and sustain heterotrophic activity (95% confidence level). Our results reveal that solid carbohydrates have a significant negative impact (95% confidence level) on CO2 production in frozen boreal spruce forest soils, in contrast to the positive effects of carbohydrate polymers during unfrozen conditions. We conclude that the hierarchy of environmental factors controlling SOM mineralization changes as soils freeze. The effect of SUM composition on pore size distribution and unfrozen water content has a superior influence on SUM mineralization and hence on heterotrophic CO2 production of frozen soils. (C) 2010 Elsevier Ltd. All rights reserved.

  • 9.
    Erhagen, Björn
    et al.
    Department of Forest Ecology & Management, Swedish University of Agricultural Sciences (SLU), Umeå, Sweden.
    Öquist, Mats
    Department of Forest Ecology & Management, Swedish University of Agricultural Sciences (SLU), Umeå, Sweden.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Haei, Mahsa
    Department of Forest Ecology & Management, Swedish University of Agricultural Sciences (SLU), Umeå, Sweden.
    Ilstedt, Ulrik
    Department of Forest Ecology & Management, Swedish University of Agricultural Sciences (SLU), Umeå, Sweden.
    Hedenström, Mattias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Schleucher, Jürgen
    Umeå University, Faculty of Medicine, Department of Medical Biochemistry and Biophysics.
    Nilsson, Mats B
    Department of Forest Ecology & Management, Swedish University of Agricultural Sciences (SLU), Umeå, Sweden.
    Temperature response of litter and soil organic matter decomposition is determined by chemical composition of organic material2013In: Global Change Biology, ISSN 1354-1013, E-ISSN 1365-2486, Vol. 19, no 12, p. 3858-3871Article in journal (Refereed)
    Abstract [en]

    The global soil carbon pool is approximately three times larger than the contemporary atmospheric pool, therefore even minor changes to its integrity may have major implications for atmospheric CO2 concentrations. While theory predicts that the chemical composition of organic matter should constitute a master control on the temperature response of its decomposition, this relationship has not yet been fully demonstrated. We used laboratory incubations of forest soil organic matter (SOM) and fresh litter material together with NMR spectroscopy to make this connection between organic chemical composition and temperature sensitivity of decomposition. Temperature response of decomposition in both fresh litter and SOM was directly related to the chemical composition of the constituent organic matter, explaining 90% and 70% of the variance in Q10 in litter and SOM respectively. The Q10 of litter decreased with increasing proportions of aromatic and O-aromatic compounds, and increased with increased contents of alkyl- and O-alkyl carbons. In contrast, in SOM, decomposition was affected only by carbonyl compounds. To reveal why a certain group of organic chemical compounds affected the temperature sensitivity of organic matter decomposition in litter and SOM, a more detailed characterisation of the (13) C aromatic region using Heteronuclear Single Quantum Coherence (HSQC) was conducted. The results revealed considerable differences in the aromatic region between litter and SOM. This suggests that the correlation between chemical composition of organic matter and the temperature response of decomposition differed between litter and SOM. The temperature response of soil decomposition processes can thus be described by the chemical composition of its constituent organic matter, this paves the way for improved ecosystem modelling of biosphere feedbacks under a changing climate.

  • 10. Filippov, Andrey
    et al.
    Munavirov, Bulat
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Ishmuhametova, Valentina
    Rudakova, Maya
    Shriram, Prashant
    Umeå University, Faculty of Medicine, Department of Pharmacology and Clinical Neuroscience, Clinical Pharmacology.
    Tavelin, Staffan
    Umeå University, Faculty of Medicine, Department of Pharmacology and Clinical Neuroscience, Clinical Pharmacology.
    Interaction of a poly(acrylic acid) oligomer with dimyristoylphosphatidylcholine bilayers2011In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 27, no 7, p. 3754-3761Article in journal (Refereed)
    Abstract [en]

    We studied the influence of 5 kDa poly(acrylic acid) (PAA) on the phase state, thermal properties, and lateral diffusion in bilayered systems of dimyristoylphosphatidylcholine (DMPC) using (31)P NMR spectroscopy, differential scanning calorimetry (DSC), (1)H NMR with a pulsed field gradient, and (1)H nuclear Overhauser enhancement spectroscopy (NOESY). The presence of PAA does not change the lamellar structure of the system. (1)H MAS NOESY cross-peaks observed for the interaction between lipid headgroups and polyion protons demonstrated only surface PAA-biomembrane interaction. Small concentrations of PAA (up to ∼4 mol %) lead to the appearance of a new lateral phase with a higher main transition temperature, a lower cooperativity, and a lower enthalpy of transition. Higher concentrations lead to the disappearance of measurable thermal effects. The lateral diffusion coefficient of DMPC and the apparent activation energy of diffusion gradually decreased at PAA concentrations up to around 4 mol %. The observed effects were explained by the formation of at least two types of PAA-DMPC lateral complexes as has been described earlier (Fujiwara, M.; Grubbs, R. H.; Baldeschwieler, J. D. J. Colloid Interface Sci., 1997, 185, 210). The first one is characterized by a stoichiometry of around 28 lipids per polymer, which corresponds to the adsorption of the entire PAA molecule onto the membrane. Lipid molecules of the complex are exchanged with the "pure" lipid bilayer, with the lifetime of the complex being less than 0.1 s. The second type of DMPC-PAA complex is characterized by a stoichiometry of 6 to 7 lipids per polymer and contains PAA molecules that are only partially adsorbed onto the membrane. A decrease in the DMPC diffusion coefficient and activation energy for diffusion in the presence of PAA was explained by the formation of a new cooperative unit for diffusion, which contains the PAA molecule and several molecules of lipids.

  • 11. Harrysson Drotz, Stina
    et al.
    Tilston, Emma L
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Schleucher, Jürgen
    Umeå University, Faculty of Medicine, Department of Medical Biochemistry and Biophysics.
    Contributions of matric and osmotic potentials to the unfrozen water content of frozen soils2009In: Geoderma, ISSN 0016-7061, E-ISSN 1872-6259, Vol. 148, no 3-4, p. 392-8Article in journal (Refereed)
    Abstract [en]

    Recent reports show that biogeochemical processes continue when the soil is frozen, but are limited by water availability. However, there is little knowledge about the interactive effects of soil and environmental variables on amounts of unfrozen water in frozen soils. The aims of this study were to determine the contributions of matric and osmotic potentials to the unfrozen water content of frozen soil. We determined the effects of matric and osmotic potential on unfrozen water contents of frozen mineral soil fractions (ranging from coarse sand to fine silt) at − 7 °C, and estimated the contributions of these potentials to liquid water contents in samples from organic surface layers of boreal soils frozen at − 4 °C. In the mineral soil fractions the unfrozen water contents appeared to be governed solely by the osmotic potential, but in the humus layers of the sampled boreal soils both the osmotic and matric potentials control unfrozen water content, with osmotic potential contributing 20 to 69% of the total water potential. We also determined pore size equivalents, where unfrozen water resides at − 4 °C, and found a strong correlation between these equivalents and microbial CO2 production. The larger the pores in which the unfrozen water is found the larger the microbial activity that can be sustained. The osmotic potential may therefore be a key determinant of unfrozen water and carbon dynamics in frozen soil.

  • 12.
    Huang, Yang
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Wang, Young-lei
    Laaksonen, Aatto
    Arrhenius Laboratory, Stockholm University, Sweden .
    Westlund, Per-Olof
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Analysis of proton/fluoride spin-lattice NMR dispersion experiment of an ionic liquid, BMIM[PF6] by using molecular dynamics simulations and relaxation theory2015Manuscript (preprint) (Other academic)
    Abstract [en]

    Proton/Fluoride spin-lattice nuclear magnetic relaxation dispersion(NMRD) measurements of 1-Butyl-3-methylimidazolium-hexa fluorophosphate (BMIM[PF6])have been carried out using a 1T Stelar FFC2000 fast-field-cycling instrument at proton Larmor frequencies ranging from 10 kHz to 40 MHz and at different temperatures. The NMRD profiles are interpreted by means of a simple relaxation modelbased on the inter- and intra-molecular dipole dipole relaxation mechanims. Using an atomic and a coarse-grained (CG)Molecular Dynamics (MD) simulations at temperature 323 K the relevant dipole-dipole correlation functions are calculated. The result indicate that the NMRD profiles can be rationalized using a combination of intra and inter molecular dipole-dipole couplings. However, both are mainly modulated by molecular reorientation whereas translation diffusion plays a minor role. The molecular reorientation dynamics  of BMIM[PF6] ,BMIM+ ion are in the nano secondtime regime whereas the reorientation of  [PF6]- is much faster and loses its correlation in the ps regime. The relaxation mechanism for  [PF6]- is H-F inter-molecular dipole-dipole coupling which is modulated by the reorientation of  the H-containing molecule.

  • 13. Lendel, Christofer
    et al.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Mayzel, Maxim
    Andersson, C. Evalena
    Karlsson, Göran
    Härd, Torleif
    Combined Solution- and Magic Angle Spinning NMR Reveals Regions of Distinct Dynamics in Amyloid β Protofibrils2016In: ChemistrySelect, ISSN 2365-6549, Vol. 1, no 18, p. 5850-5853Article in journal (Refereed)
    Abstract [en]

    Solid-state magic angle spinning (MAS) NMR has emerged as an important tool for investigations of protein aggregates and amyloid fibrils, which are not accessible for solution NMR experiments. We recently presented a structural model for amyloid β (Aβ) protofibrils based on MAS-NMR data. The absence of resonances for the N-terminus of Aβ in this dataset suggested that it might be disordered and more dynamic than the structural core. We here provide evidence for a distinct dynamic regime in the N-terminal part of the peptide and show that the structural characteristics of this region can be elucidated using 13C-detected solution NMR. The results shed more light on the structural properties of pre-fibrillar Aβ species and demonstrate the potential of combining MAS and solution NMR experiments for the characterization of structure and dynamics of complex protein assemblies.

  • 14.
    Lidman, Martin
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Dingeldein, Artur
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Pokorná, Šárka
    Šachl, Radek
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Hof, Martin
    Gröbner, Gerhard
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    The Role of Lipids in Regulation of Programmed Cell Death2016In: Biophysical Journal, ISSN 0006-3495, E-ISSN 1542-0086, Vol. 110, no 3, p. 473A-473AArticle in journal (Refereed)
  • 15.
    Lidman, Martin
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Pokorná, Šárka
    Dingeldein, Artur P. G.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Wallgren, Marcus
    Umeå University, Faculty of Medicine, Department of Medical Biochemistry and Biophysics.
    Šachl, Radek
    Hof, Martin
    Gröbner, Gerhard
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    The oxidized phospholipid PazePC promotes permeabilization of mitochondrial membranes by Bax2016In: Biochimica et Biophysica Acta - Biomembranes, ISSN 0005-2736, E-ISSN 1879-2642, Vol. 1858, no 6, p. 1288-1297Article in journal (Refereed)
    Abstract [en]

    Mitochondria play a crucial role in programmed cell death via the intrinsic apoptotic pathway, which is tightly regulated by the B-cell CLL/lymphoma-2 (Bcl-2) protein family. Intracellular oxidative stress causes the translocation of Bax, a pro-apoptotic family member, to the mitochondrial outer membrane (MOM) where it induces membrane permeabilization. Oxidized phospholipids (OxPls) generated in the MOM during oxidative stress directly affect the onset and progression of mitochondria-mediated apoptosis. Here we use MOM-mimicking lipid vesicles doped with varying concentrations of 1-palmitoyl-2-azelaoyl-sn-glycero-3-phosphocholine (PazePC), an OxPl species known to significantly enhance Bax-membrane association, to investigate three key aspects of Bax's action at the MOM: 1) induction of Bax pores in membranes without additional mediator proteins, 2) existence of a threshold OxPl concentration required for Bax-membrane action and 3) mechanism by which PazePC disturbs membrane organization to facilitate Bax penetration. Fluorescence leakage studies revealed that Bax-induced leakage, especially its rate, increased with the vesicles' PazePC content without any detectable threshold neither for OxPl nor Bax. Moreover, the leakage rate correlated with the Bax to lipid ratio and the PazePC content. Solid state NMR studies and calorimetric experiments on the lipid vesicles confirmed that OxPl incorporation disrupted the membrane's organization, enabling Bax to penetrate into the membrane. In addition, 15N cross polarization (CP) and insensitive nuclei enhanced by polarization transfer (INEPT) MAS NMR experiments using uniformly 15N-labeled Bax revealed dynamically restricted helical segments of Bax embedded in the membrane, while highly flexible protein segments were located outside or at the membrane surface.

  • 16.
    Lindgren, Matteus
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Westlund, Per-Olof
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    A combined molecular dynamic simulation and Urea 14N NMR relaxation study of the Urea - lysozyme system2010In: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy, ISSN 1386-1425, E-ISSN 1873-3557, Vol. 75, no 3, p. 953-9Article in journal (Refereed)
    Abstract [en]

    Urea in the lysozyme solvation shell has been studied by utilizing a combination of urea , water NMR relaxation experiments and a molecular dynamics simulation of the urea–lysozyme system. Samples with lysozyme in the native fold in water as well as in 3 M urea have been studied, as well as denatured lysozyme in a 8.5 M urea solvent. The spin relaxation rates of the samples with folded protein show a clear field dependence, which is consistent with a few urea molecules having long residence times on the protein surface and preferentially located in pockets and grooves on the protein. By combining the 3 M urea NMR relaxation data and data from the MD simulation, a full parameter set of the relaxation model is found which can successfully predict the experimental relaxation rates of the 3 M urea sample. However, in the parameter fitting it is evident that the rotational dynamics of urea in the MD simulation is slightly too fast to be consistent with the NMR relaxation rates, perhaps a result of the fast dynamics of the TIP3P water model. The relaxation rates of urea in the proximity of the unfolded lysozyme lack field dependence, which can be interpreted as a loss of pockets and grooves on the denatured protein. The extracted model parameters from the 3 M sample are adjusted and tested on a simple model of the unfolded protein sample and are seen to be in agreement with the relaxation rates. It is shown that the combination of NMR relaxation and MD simulations can be used to create a microscopic picture of the solvent at the protein interface, which can be used for example in the study of chemical denaturation.

  • 17.
    Lindström, Fredrick
    et al.
    Umeå University, Faculty of Science and Technology, Chemistry.
    Bokvist, Marcus
    Umeå University, Faculty of Science and Technology, Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Chemistry.
    Gröbner, Gerhard
    Umeå University, Faculty of Science and Technology, Chemistry.
    Association of amyloid-β peptide with membrane surfaces monitored by solid state NMR2002In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 4, no 22, p. 5524-5530Article in journal (Refereed)
    Abstract [en]

    Amyloid-β peptide (Aβ), a key substance in Alzheimers disease (AD), is characterized by its abnormal folding into neurotoxic aggregates. Since Aβ comprises an extracellular and transmembrane domain, some of its neurotoxic actions might be exerted via interactions with neuronal membranes. Wideline and magic angle spinning 14N and 31P NMR have been used in combination with differential scanning calorimetry and circular dichroism spectroscopy to investigate the association between Aβ1–40 peptide and membranes with different electrostatic surface potentials. Calorimetric measurements showed that all membrane systems were in the liquid crystalline state at 308 K. Binding of Aβ1–40 at a 30 1 lipid/peptide ratio to membranes composed of neutral dimyristoyl-phosphatidylcholine (DMPC) and negatively charged dimyristoylphosphatidylglycerol (DMPG) at a 4 : 1 molar ratio is mainly driven electrostatically, reflected in characteristic changes of the isotropic 31P chemical shift values for both lipids. In addition, the average orientation of the choline headgroup of DMPC, with its electric P–N+(CH3)3 dipole, changed directly in response to the reduced negative membrane surface potential. The deviation in tilt angle of the PN vector relative to the membrane surface is manifested in the observed 14N NMR quadrupole splitting and can therefore be described semiquantitatively. Adding Aβ1–40 to membranes with nominal neutral surface charge, but composed of a ternary mixture of DMPC with DMPG and the cationic amphiphile didodecyldimethyl–ammonium bromide (DDAB) at a 3 : 1 : 1 molar ratio revealed surprisingly electrostatic interactions visible in the NMR spectra. Since Aβ1–40 does not bind to neutral DMPC bilayers a model is proposed, in which on a molecular level the charged residues of Aβ1–40 peptide can interact independently with lipid headgroups of various charges in these microscopically heterogeneous systems.

  • 18. Maljanen, M
    et al.
    Virkajärvi, P
    Hytönen, J
    Öquist, M
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Chemistry.
    Martikainen, P J
    Nitrous oxide production in boreal soils with variable organic matter content at low temperature – snow manipulation experiment2009In: Biogeosciences, ISSN 1726-4170, E-ISSN 1726-4189, Vol. 6, no 11, p. 2461-73Article in journal (Refereed)
    Abstract [en]

    Agricultural soils are the most important sources for the greenhouse gas nitrous oxide (N2O), which is produced and emitted from soils also at low temperatures. The processes behind emissions at low temperatures are still poorly known. Snow is a good insulator and it keeps soil temperature rather constant. To simulate the effects of a reduction in snow depth on N2O emission in warming climate, snow pack was removed from experimental plots on three different agricultural soils (sand, mull, peat). Removal of snow lowered soil temperature and increased the extent and duration of soil frost in sand and mull soils. This led to enhanced N2O emissions during freezing and thawing events. The cumulative emissions during the first year when snow was removed over the whole winter were 0.25, 0.66 and 3.0 g N2O-N m−2 yr−1 in control plots of sand, mull and peat soils, respectively. In the treatment plots, without snow cover, the respective cumulative emissions were 0.37, 1.3 and 3.3 g N2O-N m−2 yr−1. Shorter snow manipulation during the second year did not increase the annual emissions. Only 20% of the N2O emission occurred during the growing season. Thus, these results highlight the importance of the winter season for this exchange and that the year-round measurements of annual N2O emissions from boreal soils are integral for estimating their N2O source strength. N2O accumulated in the frozen soil during winter and the soil N2O concentration correlated with the depth of frost but not with the winter N2O emission rates per se. Also laboratory incubations of soil samples showed high production rates of N2O at temperatures below 0°C, especially in the sand and peat soils.

  • 19.
    Nguyen, Anh Mai
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Dinh, Ngoc Phuoc
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Cam, Quach Minh
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Irgum, Knut
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Preparation and characterization of sizable macroporous epoxy resin-based monolithic supports for flow-through systems2009In: Journal of Separation Science, ISSN 1615-9306, E-ISSN 1615-9314, Vol. 32, no 15-16, p. 2608-2618Article in journal (Refereed)
    Abstract [en]

    This paper presents further results from our efforts to prepare sizable macroporous monolithic materials from epoxy resins and polyamines by emulsion polymerization. For their uses as supports in flow systems, the study aimed at developing materials possessing maximum fluid permeability, high mechanical stability, and a controlled porosity and surface area. Characterization of the materials has been carried out using different techniques, focusing on morphological and mechanical features, and on the surface chemistry. Morphology and porosity were studied with SEM, nitrogen adsorption/desorption, mercury intrusion porosimetry (MIP), and (2)H NMR cryoporosimetry. The chemical composition of the bulk structures and their surfaces was studied by means of bulk elemental analysis and X-ray photoelectron spectroscopy, and potentiometric titration was used to assess the relative amounts of amines and epoxy groups. Essentially, the morphological features were a high fluid permeability, but rather low specific surface area. Convective flow was facilitated by large, interconnected, and evenly spaced macropores which were formed by nonporous skeletons of the connected-rod type. Despite the interfacial nature of the polymerization, the bulk and the surface of the fully cured materials showed similar elemental compositions. All materials were found to have a high surface density of hydroxyl groups, which facilitates functionalization reactions.

  • 20. Pawar, Prashant Mohan-Anupama
    et al.
    Derba-Maceluch, Marta
    Chong, Sun-Li
    Gandla, Madhavi Latha
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Bashar, Shamrat Shafiul
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Ahvenainen, Patrik
    Hedenström, Mattias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Ozparpucu, Merve
    Ruggeberg, Markus
    Serimaa, Ritva
    Lawoko, Martin
    Tenkanen, Maija
    Jönsson, Leif J.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Mellerowicz, Ewa J.
    In muro deacetylation of xylan affects lignin properties and improves saccharification of aspen wood2017In: Biotechnology for Biofuels, ISSN 1754-6834, E-ISSN 1754-6834, Vol. 10, article id 98Article in journal (Refereed)
    Abstract [en]

    Background: Lignocellulose from fast growing hardwood species is a preferred source of polysaccharides for advanced biofuels and “green” chemicals. However, the extensive acetylation of hardwood xylan hinders lignocellulose saccharification by obstructing enzymatic xylan hydrolysis and causing inhibitory acetic acid concentrations during microbial sugar fermentation. To optimize lignocellulose for cost-effective saccharification and biofuel production, an acetyl xylan esterase AnAXE1 from Aspergillus niger was introduced into aspen and targeted to cell walls.

    Results: AnAXE1-expressing plants exhibited reduced xylan acetylation and grew normally. Without pretreatment, their lignocellulose yielded over 25% more glucose per unit mass of wood (dry weight) than wild-type plants. Glucose yields were less improved (+7%) after acid pretreatment, which hydrolyses xylan. The results indicate that AnAXE1 expression also reduced the molecular weight of xylan, and xylan–lignin complexes and/or lignin co-extracted with xylan, increased cellulose crystallinity, altered the lignin composition, reducing its syringyl to guaiacyl ratio, and increased lignin solubility in dioxane and hot water. Lignin-associated carbohydrates became enriched in xylose residues, indicating a higher content of xylo-oligosaccharides.

    Conclusions: This work revealed several changes in plant cell walls caused by deacetylation of xylan. We propose that deacetylated xylan is partially hydrolyzed in the cell walls, liberating xylo-oligosaccharides and their associated lignin oligomers from the cell wall network. Deacetylating xylan thus not only increases its susceptibility to hydrolytic enzymes during saccharification but also changes the cell wall architecture, increasing the extractability of lignin and xylan and facilitating saccharification.

  • 21. Pawar, Prashant Mohan-Anupama
    et al.
    Ratke, Christine
    Balasubramanian, Vimal K.
    Chong, Sun-Li
    Gandla, Madhavi Latha
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Adriasola, Mathilda
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Hedenstrom, Mattias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Szwaj, Klaudia
    Derba-Maceluch, Marta
    Gaertner, Cyril
    Mouille, Gregory
    Ezcurra, Ines
    Tenkanen, Maija
    Jonsson, Leif J.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Mellerowicz, Ewa J.
    Downregulation of RWA genes in hybrid aspen affects xylan acetylation and wood saccharification2017In: New Phytologist, ISSN 0028-646X, E-ISSN 1469-8137, Vol. 214, p. 1491-1505Article in journal (Refereed)
    Abstract [en]

    High acetylation of angiosperm wood hinders its conversion to sugars by glycoside hydrolases, subsequent ethanol fermentation and (hence) its use for biofuel production. We studied the REDUCED WALL ACETYLATION (RWA) gene family of the hardwood model Populus to evaluate its potential for improving saccharification. The family has two clades, AB and CD, containing two genes each. All four genes are expressed in developing wood but only RWA-A and -B are activated by master switches of the secondary cell wall PtNST1 and PtMYB21. Histochemical analysis of promoter:: GUS lines in hybrid aspen (Populus tremula x tremuloides) showed activation of RWA-A and -B promoters in the secondary wall formation zone, while RWA-C and -D promoter activity was diffuse. Ectopic downregulation of either clade reduced wood xylan and xyloglucan acetylation. Suppressing both clades simultaneously using the wood-specific promoter reduced wood acetylation by 25% and decreased acetylation at position 2 of Xylp in the dimethyl sulfoxide-extracted xylan. This did not affect plant growth but decreased xylose and increased glucose contents in the noncellulosic monosaccharide fraction, and increased glucose and xylose yields of wood enzymatic hydrolysis without pretreatment. Both RWA clades regulate wood xylan acetylation in aspen and are promising targets to improve wood saccharification.

  • 22.
    Rogne, Per
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Anugwom, Ikenna
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Mikkola, Jyri-Pekka
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Laboratory of Industrial Chemistry and Reaction Engineering, Johan Gadolin Process Chemistry Centre, Åbo Akademi University, Åbo-Turku, Finland.
    Wolf-Watz, Magnus
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Real-time 31P NMR investigation on the catalytic behavior of the enzyme Adenylate kinase in the matrix of a switchable ionic liquid2015In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 8, no 2, p. 3764-3768Article in journal (Refereed)
    Abstract [en]

    The integration of highly efficient enzymatic catalysis with the solvation properties of ionic liquids for an environmentally friendly and efficient use of raw materials such as wood requires fundamental knowledge about the influence of relevant ionic liquids on enzymes. Switchable ionic liquids (SIL) are promising candidates for implementation of enzymatic treatments of raw materials. One industrially interesting SIL is constituted by monoethanol amine (MEA) and 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) formed with sulfur dioxide (SO2) as the coupling media (DBU-SO2-MEASIL). It has the ability to solubilize the matrix of lignocellulosic biomass while leaving the cellulose backbone intact. Using a novel 31P  NMR-based real-time assay we show that this SIL is compatible with enzymatic catalysis because a model enzyme, adenylate kinase, retains its activity in up to at least 25 wt % of DBU-SO2-MEASIL. Thus this SIL appears suitable for, for example, enzymatic degradation of hemicellulose.

  • 23. Rowat, Amy C.
    et al.
    Brask, Jesper
    Sparrman, Tobias
    Umeå University, Faculty of Medicine, Medical Biochemistry and Biophsyics.
    Jensen, Knud J.
    Umeå University, Faculty of Science and Technology, Chemistry.
    Lindblom, Göran
    Umeå University, Faculty of Science and Technology, Chemistry.
    Ipsen, John H.
    Commentary: Farnesylated peptides in model membranes: a biophysical investigation (vol 33, pg 300, 2003)2004In: European Biophysics Journal, Vol. 33, no 6, p. 562-3Article in journal (Refereed)
  • 24. Rowat, Amy C.
    et al.
    Brask, Jesper
    Sparrman, Tobias
    Umeå University, Faculty of Medicine, Medical Biochemistry and Biophsyics.
    Jensen, Knud J.
    Lindblom, Göran
    Faculty of Science and Technology, Chemistry.
    Ipsen, John H.
    Farnesylated peptides in model membranes: a biophysical investigation2004In: European Biophysics Journal, ISSN 0175-7571 (Print) 1432-1017 (Online), Vol. 33, no 4, p. 300-9Article in journal (Refereed)
    Abstract [en]

    Protein prenylation plays an important role in signal transduction, protein–protein interactions, and the localization and association of proteins with membranes. Using three different techniques, this study physically characterizes the interactions between model dimyristoylphosphatidylcholine membranes and a series of farnesylated peptides. Magic angle spinning nuclear Overhauser enhancement spectroscopy and differential scanning calorimetry reveal that both charged [Ac-Asn-Lys-Asn-Cys-(farnesyl)-OMe and Ac-Asn-Lys-Asn-Cys-(farnesyl)-NH2] and uncharged [Ac-Cys-(farnesyl)-OMe and farnesol] species partition into dimyristoylphosphatidylcholine bilayers. Calorimetry and vesicle fluctuation analysis of giant unilamellar vesicles show that the charged peptides modestly decrease the main gel–fluid phase transition and markedly increase the bending rigidity of large unilamellar vesicles. Uncharged species, on the other hand, dramatically decrease the main phase transition and modestly decrease the bending rigidity. No difference with carboxyl methylation is detected.

  • 25.
    Rundqvist, Louise
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Ådén, Jörgen
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Wallgren, Marcus
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Olsson, Ulrika
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Wolf-Watz, Magnus
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Noncooperative folding of subdomains in Adenylate Kinase2009In: Biochemistry, ISSN 0006-2960, E-ISSN 1520-4995, Vol. 48, no 9, p. 1911-1927Article in journal (Refereed)
    Abstract [en]

    Conformational change is regulating the biological activity of a large number of proteins and enzymes. Efforts in structural biology have provided molecular descriptions of the interactions that stabilize the stable ground states on the reaction trajectories during conformational change. Less is known about equilibrium thermodynamic stabilities of the polypeptide segments that participate in structural changes and whether the stabilities are relevant for the reaction pathway. Adenylate kinase (Adk) is composed of three subdomains: CORE, ATPlid, and AMPbd. ATPlid and AMPbd are flexible nucleotide binding subdomains where large-scale conformational changes are directly coupled to catalytic activity. In this report, the equilibrium thermodynamic stabilities of Adk from both mesophilic and hyperthermophilic bacteria were investigated using solution state NMR spectroscopy together with protein engineering experiments. Equilibrium hydrogen to deuterium exchange experiments indicate that the flexible subdomains are of significantly lower thermodynamic stability compared to the CORE subdomain. Using site-directed mutagenesis, parts of ATPlid and AMPbd could be selectively unfolded as a result of perturbation of hydrophobic clusters located in these respective subdomains. Analysis of the perturbed Adk variants using NMR spin relaxation and Cα chemical shifts shows that the CORE subdomain can fold independently of ATPlid and AMPbd; consequently, folding of the two flexible subdomains occurs independently of each other. Based on the experimental results it is apparent that the flexible subdomains fold into their native structure in a noncooperative manner with respect to the CORE subdomain. These results are discussed in light of the catalytically relevant conformational change of ATPlid and AMPbd.

  • 26. Segura, Javier H.
    et al.
    Nilsson, Mats B.
    Haei, Mahsa
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Mikkola, Jyri-Pekka
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Industrial Chemistry & Reaction Engineering, Process Chemistry Centre, Åbo.
    Gräsvik, John
    Schleucher, Jürgen
    Umeå University, Faculty of Medicine, Department of Medical Biochemistry and Biophysics.
    Öquist, Mats G.
    Microbial mineralization of cellulose in frozen soils2017In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723, Vol. 8, no 1, article id 1154Article in journal (Refereed)
    Abstract [en]

    High-latitude soils store ~40% of the global soil carbon and experience winters of up to 6 months or more. The winter soil CO2 efflux importantly contributes to the annual CO2 budget. Microorganisms can metabolize short chain carbon compounds in frozen soils. However, soil organic matter (SOM) is dominated by biopolymers, requiring exoenzymatic hydrolysis prior to mineralization. For winter SOM decomposition to have a substantial influence on soil carbon balances it is crucial whether or not biopolymers can be metabolized in frozen soils. We added 13C-labeled cellulose to frozen (−4 °C) mesocosms of boreal forest soil and followed its decomposition. Here we show that cellulose biopolymers are hydrolyzed under frozen conditions sustaining both CO2 production and microbial growth contributing to slow, but persistent, SOM mineralization. Given the long periods with frozen soils at high latitudes these findings are essential for understanding the contribution from winter to the global carbon balance.

  • 27.
    Shimizu, Kenichi
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford, UK.
    Driver, Gordon W.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Lucas, Marie
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Shchukarev, Andrey
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Bifluoride ([HF2](-)) formation at the fluoridated aluminium hydroxide/water interface2016In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 45, no 22, p. 9045-9050Article in journal (Refereed)
    Abstract [en]

    This study uncovers bifluoride-type (difluorohydrogenate(I); [HF2](-)) species formed at mineral/water interfaces. Bifluoride forms at equivalent to Al-F surface sites resulting from the partial fluoridation of gibbsite (gamma-Al(OH3)) and bayerite (alpha-Al(OH3)) particles exposed to aqueous solutions of 50 mM NaF. Fluoride removal from these solutions is proton-promoted and results in a strongly self-buffered suspensions at circumneutral pH, proceeds at a F : H consumption ratio of 2 : 1, and with recorded losses of up to 17 mM fluoride (58 F nm(-2)). These loadings exceed crystallographic site densities by a factor of 3-4, yet the reactions have no resolvable impact on particle size, shape and mineralogy. X-ray photoelectron spectroscopy (XPS) of frozen (-155 degrees C) wet mineral pastes revealed coexisting surface F- and HF0 species. Electron energy loss features pointed to multilayer distribution of these species at the mineral/water interface. XPS also uncovered a distinct form of Na+ involved in binding fluoride-bearing species. XPS and solid state magic angle spinning F-19 nuclear magnetic resonance measurements showed that these fluoride species were highly comparable to a sodium-bifluoride (NaHF2) reference. First layer surface species are represented as =Al-F-H-F-Al= and =Al-F-Na-F-Al=, and may form multi-layered species into the mineral/water interface. These results consequently point to a potentially overlooked inorganic fluorine species in a technologically relevant mineral/water interfacial systems.

  • 28. Song, Yu
    et al.
    Jiang, Tao
    Liem-Nguyen, Van
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Björn, Erik
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Skyllberg, Ulf
    Thermodynamics of Hg(II) bonding to thiol groups in Suwannee River natural organic matter resolved by competitive ligand exchange, Hg L-III-Edge EXAFS and H-1 NMR spectroscopy2018In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 52, no 15, p. 8292-8301Article in journal (Refereed)
    Abstract [en]

    A molecular level understanding of the thermodynamics and kinetics of the chemical bonding between mercury, Hg(II), and natural organic matter (NOM) associated thiol functional groups (NOM-RSH) is required if bioavailability and transformation processes of Hg in the environment are to be fully understood. This study provides the thermodynamic stability of the Hg(NOM-RS)(2) structure using a robust method in which cysteine (Cys) served as a competing ligand to NOM (Suwannee River 2R101N sample) associated RSH groups. The concentration of the latter was quantified to be 7.5 +/- 0.4 mu mol g(-1) NOM by Hg L-III-edge EXAFS spectroscopy. The Hg(Cys)(2) molecule concentration in chemical equilibrium with the Hg(II)-NOM complexes was directly determined by HPLC-ICPMS and losses of free Cys due to secondary reactions with NOM was accounted for in experiments using H-1 NMR spectroscopy and C-13 isotope labeled Cys. The log K +/- SD for the formation of the Hg(NOM-RS)(2) molecular structure, Hg2+ + 2NOM-RS- = Hg(NOM-RS)(2), and for the Hg(Cys)(NOM-RS) mixed complex, Hg2+ + Cys(-) + NOM-RS- = Hg(Cys)(NOM-RS), were determined to be 40.0 +/- 0.2 and 38.5 +/- 0.2, respectively, at pH 3.0. The magnitude of these constants was further confirmed by H-1 NMR spectroscopy and the Hg(NOM-RS)(2) structure was verified by Hg L-III-edge EXAFS spectroscopy. An important finding is that the thermodynamic stabilities of the complexes Hg(NOM-RS)(2), Hg(Cys)(NOM-RS) and Hg(Cys)(2) are very similar in magnitude at pH values <7, when all thiol groups are protonated. Together with data on 15 low molecular mass (LMM) thiols, as determined by the same method (Liem-Ngyuen et al. Thermodynamic stability of mercury(II) complexes formed with environmentally relevant low-molecular-mass thiols studied by competing ligand exchange and density functional theory. Environ. Chem. 2017, 14, (4), 243-253.), the constants for Hg(NOM-RS)(2) and Hg(Cys)(NOM-RS) represent an internally consistent thermodynamic data set that we recommend is used in studies where the chemical speciation of Hg(II) is determined in the presence of NOM and LMM thiols.

  • 29.
    Sparrman, Tobias
    et al.
    Umeå University, Faculty of Science and Technology, Chemistry.
    Westlund, Per-Olof
    Umeå University, Faculty of Science and Technology, Chemistry.
    An NMR line shape and relaxation analysis of heavy water powder spectra of the L, L and P phases in the DPPC/water system2003In: Physical Chemistry Chemical Physics, Vol. 5, p. 2114-21Article in journal (Refereed)
    Abstract [en]

    The 2H2O NMR powder line shapes and relaxation times, T1 and T2, of the liquid crystal L, the intermediate P and the gel L phases of dipalmitoylphosphatidylcholine (DPPC)/2H2O-system are analysed. The water structure and dynamics of the lipid/water interfaces of DPPC in the hydration regime, where all water molecules are associated to the interface, are described in terms of orientational order parameters and correlation times. The line shape of the ripple phase (P) is analysed assuming model parameters of the gel or liquid crystalline phase. The narrow line shape of the ripple phase is partly due to an extra average of the quadrupole interaction because of lateral diffusion along the curved surface, reducing the splitting with a factor 0.5–0.2 depending on the nature of the curved ripple surface. However, more importantly, an extra reduction of the quadrupole splitting may be due to the same reorganization of water, among bound sites with different signs of the order parameter, which also explains the increase in the quadrupole splitting with temperature observed in the liquid crystalline phase. The linewidths in 14N MAS NMR spectra clearly indicate slow dynamics of the polar headgroup in the ripple phase. The results indicate that the headgroup hydrations of the ripple and liquid crystalline phases are similar, while the acyl chains are still in their gel state in the ripple phase. The increased headgroup area introduces a stress, as confirmed by the slow headgroup dynamics, which causes the bilayer to curve in the ripple phase.

  • 30.
    Sparrman, Tobias
    et al.
    Umeå University, Faculty of Science and Technology, Chemistry.
    Westlund, Per-Olof
    Umeå University, Faculty of Science and Technology, Chemistry.
    H-2 NMR relaxation and line shape analysis of water in a lamellar liquid crystalline phase formed by dodecyldimethylamineoxide (DDAO) and (H2O)-H-22001In: JOURNAL OF PHYSICAL CHEMISTRY B, ISSN 1520-6106, Vol. 105, no 50, p. 12524-8Article in journal (Refereed)
    Abstract [en]

    Present study combines NMR relaxation and line shape analysis for heavy water in the lamellar liquid crystalline phase of DDAO/(2)-H2O, NMR spin-lattice, spin-spin relaxation times and the quadrupole splitting are measured at two temperatures and three different water contents in the hydration regime. A molecular picture of water hydration of the DDAO/(2)-H2O interface is extracted, which indicates a much more rapid water translational diffusion along the detergent interface, as compared to phospholipid interfaces. The local order and dynamics of the bound water are, however, not changing much between the two interfaces. This indicates, that local interactions of water with the headgroup are not much dependent on the actual phase or detergent system. This work also presents clear experimental evidence for a dip at the magic angle of the H-2 powder spectrum, as theoretically predicted. Raising the temperature removes this observed dip at the isotropic frequency. This corresponds to an increase in the correlation time tau (c) from 8.5 ns at 25 degreesC to 20 ns at 55 degreesC, where tau (c) is related to translational dynamics of water along the detergent/water interface. However, this counter-intuitive increase in tau (c) with temperature may be interpreted as a reorganization of water at the interface, as is further supported by increasing quadrupolar splittings with increasing temperature.

  • 31. Sparrman, Tobias
    et al.
    Öquist, M
    Klemedtsson, L
    Schleucher, Jürgen
    Umeå University, Faculty of Medicine, Department of Medical Biochemistry and Biophysics.
    Nilsson, M
    Quantifying unfrozen water in frozen soil by high-field 2H NMR2004In: Environmental Science & Technology, Vol. 38, no 20, p. 5420-5Article in journal (Refereed)
  • 32.
    Strandberg, Erik
    et al.
    Umeå University, Faculty of Science and Technology, Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Chemistry.
    Lindblom, Göran
    Umeå University, Faculty of Science and Technology, Chemistry.
    Phase diagrams of systems with cationic α-helical membrane-spanning model peptides and dioleoylphosphatidylcholine2001In: Advances in Colloid and Interface Science, Vol. 89-90, no 239-61Article in journal (Refereed)
    Abstract [en]

    Ternary phase diagrams have been constructed of systems with dioleoylphosphatidylcholine (DOPC) and water, and two α-helical membrane-spanning model peptides, KKLAKK16[KK(LA)6KK] and KKLAKK20[KK(LA)8KK]. It was found that these peptides induced non-lamellar liquid crystalline phases. The amount of peptide needed for this phase transition depended on the water content and the temperature; and for KKLAKK16, a smaller amount of peptide was needed to induce non-lamellar phases than for KKLAKK20. Both peptides were found to induce an isotropic phase, and KKLAKK16 also induced a reversed hexagonal phase. Both peptides may also reside in a lamellar (Lα) phase. When magic angle spinning (MAS) 31P NMR experiments were performed on samples containing the Lα phase and an isotropic phase, four different isotropic chemical shifts were observed. The isotropic chemical shifts could be assigned to the phases, using spinning sidebands to calculate the chemical shift anisotropy (CSA) corresponding to each isotropic shift. MAS 13C NMR also indicated a difference in the aggregational state of the peptides between the Lα and isotropic phases. The phase diagrams were compared to the phase diagram of a similar model peptide, AWW(LA)5WWA in systems with DOPC and water. It was concluded that the phase behaviour was influenced by both electrostatic interactions between the peptides and the lipid headgroups, and the difference between the hydrophobic length of the peptide and the hydrophobic thickness of the lipid bilayer.

  • 33. Tilston, E L
    et al.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Öquist, M G
    Unfrozen water content moderates temperature dependence of sub-zero microbial respiration2010In: Soil Biology and Biochemistry, ISSN 0038-0717, E-ISSN 1879-3428, Vol. 42, no 9, p. 1396-1407Article in journal (Refereed)
    Abstract [en]

    Abrupt increases in the temperature sensitivity of soil respiration below 0 °C have been interpreted as a change in the dominance of other co-dependent environmental controls, such as the availability of liquid-state water. Yet the relationship between unfrozen water content and soil respiration at sub-zero temperatures has received little attention because of difficulties in measuring unfrozen water contents. Using a recently-developed semi-solid 2H NMR technique the unfrozen water content present in seasonally frozen boreal forest soils was quantified and related to biotic CO2 efflux in laboratory microcosms maintained at temperatures between −0.5 and −8 °C. In both soils the unfrozen water content had an exponential relationship with temperature and was increased by addition of KCl solutions of defined osmotic potential. Approximately 13% unfrozen water was required to release the dependence of soil respiration on unfrozen water content. Depending on the osmotic potential of soil solution, this threshold unfrozen water content was associated with temperatures down to −6 °C; yet if temperature were the predictor of CO2 efflux, then the abrupt increase in the temperature sensitivity of CO2 efflux was associated with −2 °C, except in soils amended with −1500 kPa KCl which did not show any abrupt changes in temperature sensitivity. The KCl-amendments also had the effect of decreasing Q10 values and activation energies (Ea) by factors of 100 and three, respectively, to values comparable with those for soil respiration in unfrozen soil. The disparity between the threshold temperatures and the reductions in Q10 values and activation energies after KCl amendment indicates the significance of unfrozen water availability as an environmental control of equal importance to temperature acting on sub-zero soil respiration. However, this significance was diminished when soils were supplied with abundant labile C (sucrose) and the influences of other environmental controls, allied to the solubility and diffusion of respiratory substrates and gases, are considered to increase.

  • 34.
    Wikberg, Erika
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Viklund, Camilla
    Jonsson, Tobias
    Irgum, Knut
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    A 2H nuclear magnetic resonance study of the state of water in neat silica and zwitterionic stationary phases and its influence on the chromatographic retention characteristics in hydrophilic interaction high-performance liquid chromatography2011In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1218, no 38, p. 6630-6638Article in journal (Refereed)
    Abstract [en]

    (2)H NMR has been used as a tool for probing the state of water in hydrophilic stationary phases for liquid chromatography at temperatures between -80 and +4°C. The fraction of water that remained unfrozen in four different neat silicas with nominal pore sizes between 60 and 300Å, and in silicas with polymeric sulfobetaine zwitterionic functionalities prepared in different ways, could be determined by measurements of the line widths and temperature-corrected integrals of the (2)H signals. The phase transitions detected during thawing made it possible to estimate the amount of non-freezable water in each phase. A distinct difference was seen between the neat and modified silicas tested. For the neat silicas, the relationship between the freezing point depression and their pore size followed the expected Gibbs-Thomson relationship. The polymeric stationary phases were found to contain considerably higher amounts of non-freezable water compared to the neat silica, which is attributed to the structural effect that the sulfobetaine polymers have on the water layer close to the stationary phase surface. The sulfobetaine stationary phases were used alongside the 100Å silica to separate a number of polar compounds in hydrophilic interaction (HILIC) mode, and the retention characteristics could be explained in terms of the surface water structure, as well as by the porous properties of the stationary phases. This provides solid evidence supporting a partitioning mechanism, or at least of the existence of an immobilized layer of water into which partitioning could be occurring.

  • 35. Öquist, Mats G.
    et al.
    Erhagen, Björn
    Umeå University, Faculty of Science and Technology, Department of Ecology and Environmental Sciences. Department of Forest Ecology & Management, Swedish University of Agricultural Sciences (SLU), Umeå, Sweden.
    Haei, Mahsa
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Ilstedt, Ulrik
    Schleucher, Jürgen
    Umeå University, Faculty of Medicine, Department of Medical Biochemistry and Biophysics.
    Nilsson, Mats B.
    The effect of temperature and substrate quality on the carbon use efficiency of saprotrophic decomposition2017In: Plant and Soil, ISSN 0032-079X, E-ISSN 1573-5036, Vol. 414, no 1, p. 113-125Article in journal (Refereed)
    Abstract [en]

    Background and aims: Mineralization of soil organic matter (SOM) constitutes a major carbon flux to the atmosphere. The carbon use efficiency (CUE) of the saprotrophic microorganisms mineralizing SOM is integral for soil carbon dynamics. Here we investigate how the CUE is affected by temperature, metabolic conditions, and the molecular complexity of the substrate.

    Methods: We incubated O-horizon soil samples (with either 13C–glucose or 13C–cellulose) from a boreal coniferous forest at 4, 9, 14, and 19 °C, and calculated CUEs based on the amount of 13C–CO2and 13C–labelled microbial biomass produced. The effects of substrate, temperature, and metabolic conditions (representing unlimited substrate supply and substrate limitation) on CUE were evaluated.

    Results: CUE from metabolizing glucose was higher as compared to cellulose. A slight decrease in CUE with increasing temperature was observed in glucose amended samples (but only in the range 9–19 °C), but not in cellulose amended samples. CUE differed significantly with metabolic conditions, i.e. CUE was higher during unlimited growth conditions as compared to conditions with substrate limitation.

    Conclusions: We conclude that it is integral to account for both differences in CUE during different metabolic phases, as well as complexity of substrate, when interpreting temperature dependence on CUE in incubation studies.

  • 36. Öquist, Mats
    et al.
    Sparrman, Tobias
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Klemedtsson, Leif
    Harrysson Drotz, Stina
    Grip, Harald
    Schleucher, Jürgen
    Umeå University, Faculty of Medicine, Department of Medical Biochemistry and Biophysics.
    Nilsson, Mats
    Water availability controls microbial temperature responses in frozen soil CO2 production2009In: Global Change Biology, ISSN 1354-1013, E-ISSN 1365-2486, Vol. 15, no 11, p. 2715-22Article in journal (Refereed)
    Abstract [en]

    Soil processes in high-latitude regions during winter are important contributors to global carbon circulation, but our understanding of the mechanisms controlling these processes is poor and observed temperature response coefficients of CO2 production in frozen soils deviate markedly from thermodynamically predicted responses (sometimes by several orders of magnitude). We investigated the temperature response of CO2 production in 23 unfrozen and frozen surface soil samples from various types of boreal forests and peatland ecosystems and also measured changes in water content in them after freezing. We demonstrate that deviations in temperature responses at subzero temperatures primarily emanates from water deficiency caused by freezing of the soil water, and that the amount of unfrozen water is mainly determined by the quality of the soil organic matter, which is linked to the vegetation cover. Factoring out the contribution of water limitation to the CO2 temperature responses yields response coefficients that agree well with expectations based on thermodynamic theory concerning biochemical temperature responses. This partitioning between a pure temperature response and the effect of water availability on the response of soil CO2 production at low temperatures is crucial for a thorough understanding of low-temperature soil processes and for accurate predictions of C-balances in northern terrestrial ecosystems.

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