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Sparrman, Tobias
Publications (10 of 47) Show all publications
Sparrman, T., Svenningsson, L., Sahlin-Sjovold, K., Nordstierna, L., Westman, G. & Bernin, D. (2019). A revised solid-state NMR method to assess the crystallinity of cellulose. Cellulose (London), 26(17), 8993-9003
Open this publication in new window or tab >>A revised solid-state NMR method to assess the crystallinity of cellulose
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2019 (English)In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 26, no 17, p. 8993-9003Article in journal (Refereed) Published
Abstract [en]

The crystallinity of cellulose has a strong impact on various material properties. Over the years, many methods have become available to estimate the crystallinity. The purpose of this work was to revise existing NMR-based methods and to introduce a complementary NMR method related to the C-13 T-1 relaxation time. The C-13 T-1 differs by an order of magnitude for amorphous and crystalline polymers among them cellulose. We have utilized the signal boost of H-1-C-13 cross polarization and the difference in C-13 T-1 as a filter to calculate the degree of crystallinity. The evaluation of the method is based on the difference in peak integrals, which is fed into a simple equation. The method was applied to five cellulosic samples of different nature and compared the obtained degree of crystallinity with the degree estimated from deconvoluted X-ray scattering patterns. Furthermore, an attempt has been made to give a basic understanding on the origin of CP enhancement in order to validate various proposed NMR methods. With the recent progress of NMR equipment, the presented method can be automatized and applied to a series of samples using a sample changer.

Place, publisher, year, edition, pages
Springer, 2019
Keywords
Crystallinity, Cellulose, MAS, C-13 NMR, C-13 T-1, Cross-polarization
National Category
Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-165331 (URN)10.1007/s10570-019-02718-0 (DOI)000493690800003 ()
Funder
Knut and Alice Wallenberg Foundation
Available from: 2019-11-27 Created: 2019-11-27 Last updated: 2019-11-27Bibliographically approved
Shamshir, A., Sparrman, T. & Westlund, P.-O. (2019). Analysis of the behaviour of confined molecules using 2H T1 nuclear magnetic relaxation dispersion. Molecular Physics
Open this publication in new window or tab >>Analysis of the behaviour of confined molecules using 2H T1 nuclear magnetic relaxation dispersion
2019 (English)In: Molecular Physics, ISSN 0026-8976, E-ISSN 1362-3028Article in journal (Refereed) Epub ahead of print
Abstract [en]

A four-site exchange model is developed in order to explain deuterium -nuclear magnetic relaxation dispersion (NMRD) profiles of acetonitrile in silica pore systems. The four-site exchange model comprises a bulk, surface and two types of burried or cavity sites. It is found that the residence time of acetonitrile- at a flat Si-surface is less than 100 ps. No bilayer-like ordering of acetonitrile is formed at the Si-surface because no quadrupole splitting was observed. The dispersion in the deuterium T1-NMRD profiles are due to relatively few so-called beta-sites with molecular residence time in the range 0.2-2 micro seconds. This deuterium T-NMR dispersion experiment suggest that the retention time of different analysts can be studied in terms of their residence time in beta sites.

Place, publisher, year, edition, pages
Taylor & Francis, 2019
Keywords
Spin-lattice relaxation time of acetonitrile-d3, NMRD, molecular origin of the retention time, 4-site exchange model
National Category
Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-162676 (URN)10.1080/00268976.2019.1645367 (DOI)000479433000001 ()
Available from: 2019-09-02 Created: 2019-09-02 Last updated: 2020-01-08
Segura, J. H., Nilsson, M. B., Sparrman, T., Serk, H., Schleucher, J., Tolu, J. & Öquist, M. G. (2019). Boreal tree species affect soil organic matter composition and saprotrophic mineralization rates. Plant and Soil, 441(1-2), 173-190
Open this publication in new window or tab >>Boreal tree species affect soil organic matter composition and saprotrophic mineralization rates
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2019 (English)In: Plant and Soil, ISSN 0032-079X, E-ISSN 1573-5036, Vol. 441, no 1-2, p. 173-190Article in journal (Refereed) Published
Abstract [en]

Aims: To investigate how different tree species affect the composition of SOM and its mineralization in boreal forest ecosystems.

Methods: We used pyrolysis GC-MS for molecular-level characterization of the SOM formed under five common boreal tree species at a replicated field experiment similar to 50years after plantation. We incubated soil samples at 4, 9, 14 and 19 degrees C and measured inherent CO2 production and substrate-induced respiration. We then evaluated if the saprotrophic microbial activity and its temperature sensitivity was controlled by the SOM composition.

Results: The molecular composition of the SOM emerged as key factor influencing SOM properties in plots with different tree species. Most of the variance in the SOM content was explained by the organo-chemical composition of the SOM. More importantly, the fraction of the microbial community able to utilize the native SOM was largely controlled by the SOM organo-chemical composition. Temperature sensitivity of CO2 production (Q(10)) was not explained by SOM composition. However, the microbial access to different SOM pools varied with temperature.

Conclusions: These results bridge the gap between the paradigms of short-term litter and long-term SOM decomposition showing that, on an intermediate timescale (similar to 50 years), boreal tree species affect SOM molecular composition and saprotrophic mineralization rates.

Place, publisher, year, edition, pages
Springer, 2019
Keywords
Boreal forest, Soil organic matter, Organo-chemical composition, Microbial respiration, Q(10), Q(R), Pyrolysis-GC-MS
National Category
Forest Science
Identifiers
urn:nbn:se:umu:diva-163690 (URN)10.1007/s11104-019-04105-x (DOI)000482412400011 ()
Available from: 2019-10-17 Created: 2019-10-17 Last updated: 2019-10-17Bibliographically approved
Sar, S., Öqvist, L. S., Sparrman, T., Engström, F. & Samuelsson, C. (2019). Characterization of Double Leached Waelz Oxide for Identification of Fluoride Mineral. Metals, 9(3), Article ID 361.
Open this publication in new window or tab >>Characterization of Double Leached Waelz Oxide for Identification of Fluoride Mineral
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2019 (English)In: Metals, ISSN 2075-4701, Vol. 9, no 3, article id 361Article in journal (Refereed) Published
Abstract [en]

Double leached Waelz oxide (DLWO), with 76% zinc, is a secondary zinc containing raw materials obtained by the treatment of electric arc furnace dust. The content of fluoride in DLWO is still too high for direct leaching, as fluoride has a detrimental effect on electrowinning for zinc production. Knowledge of the characteristics of DLWO, and especially on how a fluoride mineral might exist, can contribute to further improvement of the selective leaching for the removal of fluoride. In this study, DLWO was characterized using analytical techniques, such as inductively coupled plasma-optical emission spectroscopy (ICP-OES), F-19 liquid-state nuclear magnetic resonance (F-19 LS NMR), X-ray powder diffraction analysis (XRD), scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) and F-19 solid-state nuclear magnetic resonance (F-19 SS NMR). This study showed that DLWO mainly consisted of zincite (ZnO), cerussite (PbCO3) and a spinel containing zinc, iron and manganese. The fluoride mineral identified was calcium fluoride (CaF2). In SEM analysis, fluorine was found in larger grains together with calcium and oxygen, which was possibly calcium carbonate.

Place, publisher, year, edition, pages
MDPI, 2019
Keywords
metal recycling, zinc secondary dust material, characterization of double leached Waelz oxide, halogens, fluoride identification
National Category
Metallurgy and Metallic Materials Geochemistry
Identifiers
urn:nbn:se:umu:diva-158593 (URN)10.3390/met9030361 (DOI)000464321200002 ()
Available from: 2019-05-27 Created: 2019-05-27 Last updated: 2019-05-27Bibliographically approved
Shamshir, A., Dinh, N. P., Jonsson, T., Sparrman, T., Ashiq, M. J. & Irgum, K. (2019). Interaction of toluene with polar stationary phases under conditions typical of hydrophilic interaction chromatography probed by saturation transfer difference nuclear magnetic resonance spectroscopy. Journal of Chromatography A, 1588, 58-67
Open this publication in new window or tab >>Interaction of toluene with polar stationary phases under conditions typical of hydrophilic interaction chromatography probed by saturation transfer difference nuclear magnetic resonance spectroscopy
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2019 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1588, p. 58-67Article in journal (Refereed) Published
Abstract [en]

Toluene has been used as void volume (zero retention) marker since the inception of hydrophilic interaction chromatography (HILIC), based on the assumption that its hydrophobicity should prevent it from interacting with stationary phases envisioned to be covered by relatively thick layers of water. Recent work has shown that the void volumes of partly water-swollen HILIC phases are not identical to the volumes probed by toluene, yet the compound is still ubiquitously used as void volume marker. As part of our investigations of the retention mechanisms in HILIC, we probed the extent to which toluene is capable of penetrating into the water-enriched layer and to interact with the functional groups of three commercially available hydrophilic and polar stationary phases with different charge properties and water-retaining abilities, using saturation transfer difference 1H nuclear magnetic resonance (STD-NMR) spectroscopy at high resolution magic angle spinning (HR-MAS) conditions. The test solutions were 1000 ppm of toluene in deuterated acetonitrile and water mixtures, with and without addition of ammonium acetate, in order to mimic a set of conditions typically encountered in HILIC separations. Interactions between toluene and the functional groups on the stationary phases were probed by equilibrating the phases with these eluent mimics and measuring the transfer of magnetization from stationary phase protons to the protons of toluene. Our results show that toluene is indeed capable of traversing the water-enriched layers of all the three tested phases and of interacting with protons that are tightly associated with the stationary phases.

Place, publisher, year, edition, pages
Elsevier, 2019
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:umu:diva-157748 (URN)10.1016/j.chroma.2018.11.028 (DOI)000461403900008 ()30704776 (PubMedID)2-s2.0-85060523282 (Scopus ID)
Funder
Swedish Research Council, 2012-4000
Available from: 2019-04-09 Created: 2019-04-09 Last updated: 2020-01-08Bibliographically approved
Segura, J. H., Nilsson, M. B., Schleucher, J., Haei, M., Sparrman, T., Székely, A., . . . Öquist, M. G. (2019). Microbial utilization of simple carbon substrates in boreal peat soils at low temperatures. Soil Biology and Biochemistry, 135, 438-448
Open this publication in new window or tab >>Microbial utilization of simple carbon substrates in boreal peat soils at low temperatures
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2019 (English)In: Soil Biology and Biochemistry, ISSN 0038-0717, E-ISSN 1879-3428, Vol. 135, p. 438-448Article in journal (Refereed) Published
Abstract [en]

Boreal peatlands are key high-latitude ecosystem types and act as a carbon (C) sink storing an estimated 25% of the world's soil C. These environments are currently seeing the most substantial changing climate, especially during the winter. CO2 emissions during the winter can correspond to 80% of the growing season's net CO2 assimilation. Yet, our conceptual understanding of the controls on microbial metabolic activity in peat soils at temperatures ≤0 °C is poor. We used stable isotope probing of peat samples and tracked the fate of 13C-glucose using 13C-NMR. We show that microorganisms in frozen boreal peat soils utilize monomeric C-substrates to sustain both catabolic and anabolic metabolism at temperatures down to −5 °C. The 13C-substrate was transformed into 13C–CO2, different metabolites, and incorporated into membrane phospholipid fatty acids. The 16S rRNA-based community analyses revealed the activity at −3 °C changes the composition of the bacterial community over relevant timescales. Below 0 °C, small temperature changes have strong effects on process rates and small differences in winter soil temperature may affect C dynamics of northern peatlands. Understanding biological processes at low and below zero temperatures are central for the overall functioning of these systems representing one of the world's major soil C pools.

Place, publisher, year, edition, pages
Elsevier, 2019
Keywords
Frozen peat soils, Microbial activity, Metabolism, C-13-NMR, DNA, Carbon cycling
National Category
Soil Science
Identifiers
urn:nbn:se:umu:diva-162400 (URN)10.1016/j.soilbio.2019.06.006 (DOI)000477689700051 ()2-s2.0-85067368525 (Scopus ID)
Available from: 2019-08-19 Created: 2019-08-19 Last updated: 2019-10-17Bibliographically approved
Dingeldein, A. P. G., Sparrman, T., Ådén, J., Wacklin, H. P., Clifton, L. A. & Gröbner, G. (2019). Mitochondrial Membrane Organization under Oxidative Stress: Insight by Solid-State NMR and Neutron Reflectometry. Paper presented at 63rd Annual Meeting of the Biophysical-Society, MAR 02-06, 2019, Baltimore, MD. Biophysical Journal, 116(3), 508A-508A
Open this publication in new window or tab >>Mitochondrial Membrane Organization under Oxidative Stress: Insight by Solid-State NMR and Neutron Reflectometry
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2019 (English)In: Biophysical Journal, ISSN 0006-3495, E-ISSN 1542-0086, Vol. 116, no 3, p. 508A-508AArticle in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
CELL PRESS, 2019
National Category
Biophysics
Identifiers
urn:nbn:se:umu:diva-157775 (URN)10.1016/j.bpj.2018.11.2742 (DOI)000460779802556 ()
Conference
63rd Annual Meeting of the Biophysical-Society, MAR 02-06, 2019, Baltimore, MD
Available from: 2019-04-10 Created: 2019-04-10 Last updated: 2019-04-10Bibliographically approved
Svenningsson, L., Sparrman, T., Bialik, E., Bernin, D. & Nordstierna, L. (2019). Molecular orientation distribution of regenerated cellulose fibers investigated with rotor synchronized solid state NMR spectroscopy. Cellulose (London), 26(8), 4681-4692
Open this publication in new window or tab >>Molecular orientation distribution of regenerated cellulose fibers investigated with rotor synchronized solid state NMR spectroscopy
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2019 (English)In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 26, no 8, p. 4681-4692Article in journal (Refereed) Published
Abstract [en]

A regenerated cellulose fiber is, in contrast to cotton, a man-made fiber. In the fiber production, the cellulose polymer is subject to various processing steps, affecting the underlying molecular orientation distribution, which is a determining factor for mechanical properties of the fiber. In this work, the molecular orientation distribution was determined in a C-13 natural abundance Lyocell regenerated cellulose fiber bundle using rotor synchronized magic angle spinning NMR spectroscopy (ROSMAS) to investigate the chemical shift anisotropy (CSA). The recorded signal intensities were compared with an analytical model of the experiment to find the order parameters reflecting the orientation of the fiber. The CSA tensor was calculated using density functional theory for the crystalline cellulose II structure, commonly found in regenerated cellulose, and is required as an input parameter. The expected order parameter values were only found when approximating the glycosidic bond and its CSA tensor as being parallel to the molecular frame with the order parameter P2=0.45 +/- 0.02 compared to P2=0.46 +/- 0.02 obtained with wide angle X-ray scattering on a fiber bundle. To make this method accessible to the community, we distribute the Matlab script for the simulation of spectra obtained by the ROSMAS experiment at github.com/LeoSvenningsson/ROSMAS.

Place, publisher, year, edition, pages
Springer, 2019
Keywords
NMR, Regenerated cellulose, Cellulose II, Oriented polymer, Molecular order, Molecular orientation, Fiber
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:umu:diva-159390 (URN)10.1007/s10570-019-02430-z (DOI)000467057500001 ()
Available from: 2019-06-10 Created: 2019-06-10 Last updated: 2019-06-10Bibliographically approved
Dingeldein, A. P. G., Sparrman, T. & Gröbner, G. (2018). Oxidatively stressed mitochondria-mimicking membranes: a molecular insight into their organization during apoptosis. Biochimica et Biophysica Acta - Biomembranes, 1860(12), 2644-2654
Open this publication in new window or tab >>Oxidatively stressed mitochondria-mimicking membranes: a molecular insight into their organization during apoptosis
2018 (English)In: Biochimica et Biophysica Acta - Biomembranes, ISSN 0005-2736, E-ISSN 1879-2642, Vol. 1860, no 12, p. 2644-2654Article in journal (Refereed) Published
Abstract [en]

Mitochondria are crucially involved in the removal of eukaryotic cells by the intrinsic pathway of programmed cell death (apoptosis). The mitochondrion's outer membrane (MOM) is the platform where this pathway takes place. Upon oxidative stress triggering apoptotic action, the MOM undergoes permeabilization and release of cytochrome c, ultimately causing cell death. This membrane perforation is regulated not only by opposing members of the Bcl-2 protein family meeting at the MOM but also actively the membrane itself. Upon oxidative damage, the membrane undergoes severe reorganization causing an increase in cell death-causing apoptotic Bcl-2 proteins. To understand the active role of MOM, we provided a detailed molecular view of its structural and dynamic reorganization upon oxidative stress by solid-state C-13 MAS NMR (magic angle spinning nuclear magnetic resonance) accompanied by calorimetric studies. By focusing on MOM-like vesicles doped with oxidized lipid species, direct polarization C-13 MAS NMR provided a quantitative overview and identification of all lipid moieties across the membrane. H-1-C-1(3) cross polarization and insensitive nuclei enhanced by polarization transfer MAS NMR generated a dynamic - mobile versus restricted - membrane profile. Oxidized phospholipids significantly perturb the structural membrane organization and increase membrane dynamics. These perturbations are not uniformly distributed as the hydrophobic core is reflecting the melting of lipid chains and increase in molecular disorder directly, whereas the interface and headgroup region undergo complex dynamical changes, reflecting increased intra-molecular flexibility of these moieties. These changes are potentially crucial in augmenting pro-apoptotic action of proteins like Bax.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Apoptosis, Oxidized lipids, Mitochondrial membranes, Solid-state NMR, Membrane dynamics, Membrane order
National Category
Biophysics
Identifiers
urn:nbn:se:umu:diva-154934 (URN)10.1016/j.bbamem.2018.10.007 (DOI)000449898900017 ()30296415 (PubMedID)
Funder
Swedish Research CouncilSwedish Cancer SocietyThe Kempe FoundationsKnut and Alice Wallenberg Foundation
Available from: 2019-01-07 Created: 2019-01-07 Last updated: 2019-01-07Bibliographically approved
Song, Y., Jiang, T., Liem-Nguyen, V., Sparrman, T., Björn, E. & Skyllberg, U. (2018). 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 spectroscopy. Environmental Science and Technology, 52(15), 8292-8301
Open this publication in new window or tab >>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 spectroscopy
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2018 (English)In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 52, no 15, p. 8292-8301Article in journal (Refereed) Published
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.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
National Category
Organic Chemistry
Identifiers
urn:nbn:se:umu:diva-151396 (URN)10.1021/acs.est.8b00919 (DOI)000441477600027 ()29983050 (PubMedID)
Funder
Swedish Research Council, 2013-6978Swedish Research Council, 621-2014-5370The Kempe Foundations, JCK-1501The Kempe Foundations, SMK-2745The Kempe Foundations, SMK-1243
Available from: 2018-09-05 Created: 2018-09-05 Last updated: 2018-09-05Bibliographically approved
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