| 1. |
- Berglund, Linn, et al.
(författare)
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Seaweed-Derived Alginate–Cellulose Nanofiber Aerogel for Insulation Applications
- 2021
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 13:29, s. 34899-34909
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Tidskriftsartikel (refereegranskat)abstract
- The next generation of green insulation materials is being developed to provide safer and more sustainable alternatives to conventional materials. Bio-based cellulose nanofiber (CNF) aerogels offer excellent thermal insulation properties; however, their high flammability restricts their application. In this study, the design concept for the development of a multifunctional and non-toxic insulation material is inspired by the natural composition of seaweed, comprising both alginate and cellulose. The approach includes three steps: first, CNFs were separated from alginate-rich seaweed to obtain a resource-efficient, fully bio-based, and inherently flame-retardant material; second, ice-templating, followed by freeze-drying, was employed to form an anisotropic aerogel for effective insulation; and finally, a simple crosslinking approach was applied to improve the flame-retardant behavior and stability. At a density of 0.015 g cm–3, the lightweight anisotropic aerogels displayed favorable mechanical properties, including a compressive modulus of 370 kPa, high thermal stability, low thermal conductivity (31.5 mW m–1 K–1), considerable flame retardancy (0.053 mm s–1), and self-extinguishing behavior, where the inherent characteristics were considerably improved by crosslinking. Different concentrations of the crosslinker altered the mechanical properties, while the anisotropic structure influenced the mechanical properties, combustion velocity, and to some extent thermal conductivity. Seaweed-derived aerogels possess intrinsic characteristics that could serve as a template for the future development of sustainable high-performance insulation materials.
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| 2. |
- Gowda, Vasantha, et al.
(författare)
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DFT calculations in the assignment of solid-state NMR and crystal structure elucidation of a lanthanum(iii) complex with dithiocarbamate and phenanthroline
- 2016
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 45:48, s. 19473-19484
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Tidskriftsartikel (refereegranskat)abstract
- The molecular, crystal, and electronic structures as well as spectroscopic properties of a mononuclear heteroleptic lanthanum(iii) complex with diethyldithiocarbamate and 1,10-phenanthroline ligands (3 : 1) were studied by solid-state 13C and 15N cross-polarisation (CP) magic-angle-spinning (MAS) NMR, X-ray diffraction (XRD), and first principles density functional theory (DFT) calculations. A substantially different powder XRD pattern and 13C and 15N CP-MAS NMR spectra indicated that the title compound is not isostructural to the previously reported analogous rare earth complexes with the space group P21/n. Both 13C and 15N CP-MAS NMR revealed the presence of six structurally different dithiocarbamate groups in the asymmetric unit cell, implying a non-centrosymmetric packing arrangement of molecules. This was supported by single-crystal X-ray crystallography showing that the title compound crystallised in the triclinic space group P1[combining macron]. In addition, the crystal structure also revealed that one of the dithiocarbamate ligands has a conformational disorder. NMR chemical shift calculations employing the periodic gauge including projector augmented wave (GIPAW) approach supported the assignment of the experimental 13C and 15N NMR spectra. However, the best correspondences were obtained with the structure where the atomic positions in the X-ray unit cell were optimised at the DFT level. The roles of the scalar and spin-orbit relativistic effects on NMR shielding were investigated using the zeroth-order regular approximation (ZORA) method with the outcome that already the scalar relativistic level qualitatively reproduces the experimental chemical shifts. The electronic properties of the complex were evaluated based on the results of the natural bond orbital (NBO) and topology of the electron density analyses. Overall, we apply a multidisciplinary approach acquiring comprehensive information about the solid-state structure and the metal-ligand bonding of the heteroleptic lanthanum complex.
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| 3. |
- Gowda, Vasantha, et al.
(författare)
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Structure Elucidation of an Yttrium Diethyldithiocarbamato-Phenanthroline Complex by X-ray Crystallography, Solid-State NMR, and ab-initio Quantum Chemical Calculations
- 2016
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; 20, s. 3278-3291
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Tidskriftsartikel (refereegranskat)abstract
- We present a structural analysis method for molecular and electronic structure of yttrium diethyldithiocarbamato-phenanthroline complex {[Y(S2CNR2)3PHEN] with R = C2H5 and PHEN = 1,10-phenanthroline} combining solid-state NMR spectroscopy, XRD, and first principles DFT calculations. Replacing the Nd3+ ion with Y3+ in the reported crystal structure of [Nd(S2CNR2)3PHEN] complex generated an approximate 3D structure of the title complex. The structure was then subjected to first principles quantum chemical geometry optimisation using periodic DFT method. The quality of the method is discussed by comparing predicted and experimental powder XRD patterns. Full assignment of 13C and 15N solid-state CP-MAS NMR spectra as well as analyses of the principal values of the chemical shift tensors were carried out using periodic scalar relativistic DFT modelling. Spin-orbit relativistic effects, estimated by SO-ZORA formalism for one molecular unit, were evaluated. Finally, the X-ray structure of the title complex was determined, which proved that the former procedure is appropriate. The most important orbital interactions were investigated by Natural Bond Orbital analysis. The isotropic shielding values for S2CN-carbons were analysed by Natural Localised Molecular Orbital analysis. The present approach can be further extended to study other rare earth metal complexes, particularly those having similar but not yet solved crystal structures
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| 4. |
- Javed, Muhammad Asadullah, et al.
(författare)
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Y Structure and dynamics elucidation of ionic liquids using multidimensional Laplace NMR
- 2017
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Ingår i: Chemical Communications. - : Royal Society of Chemistry. - 1359-7345 .- 1364-548X. ; 53:80, s. 11056-11059
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Tidskriftsartikel (refereegranskat)abstract
- We demonstrate the ability of multidimensional Laplace NMR (LNMR), comprising relaxation and diffusion experiments, to reveal essential information about microscopic phase structures and dynamics of ionic liquids that is not observable using conventional NMR spectroscopy or other techniques.
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| 5. |
- Khalili, Roya, et al.
(författare)
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129Xe NMR analysis of pore structures and adsorption phenomena in rare-earth element phosphates
- 2022
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Ingår i: Microporous and Mesoporous Materials. - : Elsevier. - 1387-1811 .- 1873-3093. ; 344
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Tidskriftsartikel (refereegranskat)abstract
- Rare-earth elements (REEs) are indispensable in various applications ranging from catalysis to batteries and they are commonly found from phosphate minerals. Xenon is an excellent exogenous NMR probe for materials because it is inert and its 129Xe chemical shift is very sensitive to its local physical or chemical environment. Here, we exploit, for the first time, 129Xe NMR for the characterization of porous structures and adsorption properties of REE phosphates (REEPO4). We study four different REEPO4 samples (REE = La, Lu, Sm and Yb), including both light (La and Sm) and heavy (Lu and Yb) as well as diamagnetic (La and Lu) and paramagnetic (Sm and Yb) REEs. 129Xe resonances are very sensitive to the porous structures and moisture content of the REEPO4 samples. In the samples treated at a lower temperature (80 °C), free water hinders the access of hydrophobic xenon into small mesopores, but the treatment at a higher temperature (200 °C) removes the free water and allows xenon to explore the mesopores. Based on a standard two-site exchange model analysis of the variable-temperature 129Xe chemical shifts, as well as its proposed, novel modification for paramagnetic materials, the average mesopore sizes were determined. The size was the largest (79 nm) for the La sample with mixed monazite (70%) and rhabdophane (30%) phases and the smallest (6 nm) for the Yb sample with pure xenotime phase. The mesopore sizes of the Lu and Yb samples (12 and 6 nm) differed by a factor of two regardless of their similar xenotime phase. The 129Xe NMR analysis revealed that the heats of adsorption of the samples are similar, varying between 8.7 and 10.1 kJ/mol. For diamagnetic samples, computational modelling confirmed the order of magnitude of the chemical shifts of Xe adsorbed on surfaces and therefore the validity of the two-site exchange model analysis. Overall, 129Xe NMR provides exceptionally versatile information about the pore structures and adsorption properties of REEPO4 materials, which may be very useful for developing the extraction processes and applications of REEs.
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| 6. |
- Khalili, Roya, et al.
(författare)
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Local structures of rare earth phosphate minerals by NMR
- 2022
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Ingår i: Journal of Solid State Chemistry. - : Elsevier. - 0022-4596 .- 1095-726X. ; 311
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Tidskriftsartikel (refereegranskat)abstract
- 31P solid state NMR studies combined with DFT calculations were conducted over a chosen series of rare earth element phosphates (REEPO4s), selected on the basis of the size and magnetic properties of REEs (La, Sm, Lu and Yb). PXRD analysis revealed the presence of rhabdophane (La, Sm), monazite (La) and xenotime (Lu, Yb) phases of these phosphate compounds. The direct excitation and cross-polarization 31P NMR studies together with calculations confirmed the PXRD results for the abovementioned bulk structures, but also revealed presence of several local phosphorus environments on surfaces. NMR is sensitive to the atomic level local interactions, and we were able to show that the combination of experimental and theoretical NMR methods can provide information unavailable with other methods. Due to the distinct coordination of the water molecules to crystal surfaces with different Miller plane cleavages, we were able to identify from the NMR spectra the surface structures of the studied minerals. This adds to the knowledge of the bulk structures of REE phosphates and provides preliminary data for studies on coordination of various ligands on REE phosphate surfaces. This combination of experimental and computational methods can further be used for studies on surface chemistry, important for applications in catalysis and extraction of REEs from the minerals.
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| 7. |
- Kotsyubynskyy, Dmytro, et al.
(författare)
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Carbon-13 NOESY and equivalent protons : methyl iodide dynamics
- 2010
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Ingår i: Journal of magnetic resonance. - : Elsevier BV. - 1090-7807 .- 1096-0856. ; 204:2, s. 239-247
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Tidskriftsartikel (refereegranskat)abstract
- We have shown that proton-coupled carbon-13 2D NOESY experiments, performed on degenerate spin systems, can provide unique quantitative information about anisotropic reorientational motions and molecular geometry. Relevant theory for AX2 and AX3 spin systems is presented, assuming the dipole–dipole and random field relaxation mechanisms of 13C nucleus, and demonstrated on methyl iodide solution in chloroform. Agreement with experimental intensities of all the six independent peaks is very good in the whole range of mixing times (up to 45 s).
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| 8. |
- Mailhiot, Sarah E., et al.
(författare)
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Melting of aqueous NaCl solutions in porous materials: shifted phase transition distribution (SIDI) approach for determining NMR cryoporometry pore size distributions
- 2024
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : The Royal Society of Chemistry. - 1463-9076 .- 1463-9084.
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Tidskriftsartikel (refereegranskat)abstract
- Nuclear magnetic resonance cryoporometry (NMRC) and differential scanning calorimetry thermoporometry (DSC-TPM) are powerful methods for measuring mesopore size distributions. The methods are based on the fact that, according to the Gibbs–Thomson equation, the melting point depression of a liquid confined to a pore is inversely proportional to the pore size. However, aqueous salt solutions, which inherently exist in a broad range of biological porous materials as well as technological applications such as electrolytes, do not melt at a single temperature. This causes artefacts in the pore size distributions extracted by traditional Gibbs–Thomson analysis of NMRC and DSC-TPM data. Bulk aqueous NaCl solutions are known to have a broad distribution of melting points between the eutectic and pure water phase transition points (252–273 K). Here, we hypothesize that, when aqueous NaCl solution (saline) is confined to a small pore, the whole melting point distribution is shifted toward lower temperatures by the value predicted by the Gibbs–Thomson equation. We show that this so-called shifted phase transition distribution (SIDI) approach removes the artefacts arising from the traditional Gibbs–Thomson analysis and gives correct pore size distributions for saline saturated mesoporous silica gel and controlled pore materials analyzed by NMR cryoporometry. Furthermore, we demonstrate that the method can be used for determining pore sizes in collagen–chondroitin sulphate hydrogels resembling the composition of the extracellular matrix of articular cartilage. It is straightforward to apply the SIDI analysis for DSC-TMP data as well.
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| 9. |
- Stark, Sari, et al.
(författare)
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Decreased soil microbial nitrogen under vegetation 'shrubification' in the subarctic forest–tundra ecotone : the potential role of increasing nutrient competition between plants and soil microorganisms
- 2023
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Ingår i: Ecosystems. - : Springer Nature. - 1432-9840 .- 1435-0629. ; 26:7, s. 1504-1523
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Tidskriftsartikel (refereegranskat)abstract
- The consequences of warming-induced ‘shrubification’ on Arctic soil carbon storage are receiving increased attention, as the majority of ecosystem carbon in these systems is stored in soils. Soil carbon cycles in these ecosystems are usually tightly coupled with nitrogen availability. Soil microbial responses to ‘shrubification’ may depend on the traits of the shrub species that increase in response to warming. Increase in deciduous shrubs such as Betula nana likely promotes a loss of soil carbon, whereas the opposite may be true if evergreen shrubs such as Empetrum hermaphroditum increase. We analyzed soil organic matter stocks and 13C NMR fractions, microbial CO2 respiration, biomass, extracellular enzyme activities (EEAs), and their association with shrub density in northern Sweden after 20 years of experimental warming using open top chambers (OTCs). Our study sites were located in a tundra heath that stores high soil carbon quantities and where the OTCs had increased deciduous shrubs, and in a mountain birch forest that stores lower soil carbon quantities and where the OTCs had increased evergreen shrubs. We predicted that organic matter stocks should be lower and respiration and EEAs higher inside the OTCs than untreated plots in the tundra, whereas no effect should be detected in the forest. Soil organic matter stocks and 13C NMR fractions remained unaffected at both sites. When expressed as per gram microbial biomass, respiration and EEAs for carbohydrate and chitin degradation were higher inside the OTCs, and contrasting our prediction, this effect was stronger in the forest. Unexpectedly, the OTCs also led to a substantially lower microbial biomass carbon and nitrogen irrespective of habitat. The decline in the microbial biomass counteracted increased activities resulting in no effect of the OTCs on respiration and a lower phenol oxidase activity per gram soil. Microbial biomass nitrogen correlated negatively with evergreen shrub density at both sites, indicating that ‘shrubification’ may have intensified nutrient competition between plants and soil microorganisms. Nutrient limitation could also underlie increased respiration per gram microbial biomass through limiting C assimilation into biomass. We hypothesize that increasing nutrient immobilization into long-lived evergreen shrubs could over time induce microbial nutrient limitation that contributes to a stability of accumulated soil organic matter stocks under climate warming.
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| 10. |
- Tolkkinen, Katja, et al.
(författare)
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SPICY : a method for single scan rotating frame relaxometry
- 2023
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 25:18, s. 13164-13169
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Tidskriftsartikel (refereegranskat)abstract
- T 1ρ is an NMR relaxation mode that is sensitive to low frequency molecular motions, making it an especially valuable tool in biomolecular research. Here, we introduce a new method, SPICY, for measuring T1ρ relaxation times. In contrast to conventional T1ρ experiments, in which the sequence is repeated many times to determine the T1ρ time, the SPICY sequence allows determination of T1ρ within a single scan, shortening the experiment time remarkably. We demonstrate the method using 1H T1ρ relaxation dispersion experiments. Additionally, we combine the sequence with spatial encoding to produce 1D images in a single scan. We show that T1ρ relaxation times obtained using the single scan approach are in good agreement with those obtained using the traditional experiments.
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