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• 1.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Chemistry. Umeå University, Faculty of Science and Technology, Department of Chemistry. Umeå University, Faculty of Science and Technology, Department of Chemistry. Umeå University, Faculty of Science and Technology, Department of Chemistry. Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, Åbo Akademi University, Piispankatu 8, FIN-20500, Turku/Åbo, Finland.
Oxidation of α-pinene over gold containing bimetallic nanoparticles supported on reducible TiO2 by DPU method2011In: Applied Catalysis A: General, ISSN 0926-860X, E-ISSN 1873-3875, Vol. 392, no 1-2, 11-18 p.Article in journal (Refereed)

A series of bimetallic catalysts Au–M (where M = Cu, Co and Ru) were supported on a reducible TiO2 oxide via deposition-precipitation (DP) method with a slow decomposition of urea as the precipitating agent. The characteristic structural features of the prepared materials were characterized by various physico-chemical techniques such as X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). XPS results indicated the formation of alloyed bimetallic particles on the TiO2 support. TEM results confirmed the fine dispersion of metal nanoparticles on the support with an average particle size in the range of 3–5 nm. An industrially important process, oxy-functionalization of α-pinene was carried out over the prepared bimetallic heterogeneous catalysts under liquid phase conditions. Reaction parameters such as the reaction time, temperature, and the effect of solvent were studied for optimal conversion of α-pinene into verbenone. The major products obtained were verbenone, verbenol, α-pinene oxide and alkyl-pinene peroxide. The activity of the catalysts followed the order; AuCu/TiO2 > AuCo/TiO2 > Cu/TiO2 > Au/TiO2 > AuRu/TiO2. Upon comparison of the various catalysts, AuCu/TiO2 was found to be an active and selective catalyst towards the formation of verbenone. The temperature, nature of the catalysts and the choice of solvents greatly influenced the reaction rate.

• 2. Alonso-Mori, R.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Towards characterization of photo-excited electron transfer and catalysis in natural and artificial systems using XFELs2016In: Faraday discussions (Online), ISSN 1359-6640, E-ISSN 1364-5498, Vol. 194, 621-638 p.Article in journal (Refereed)

The ultra-bright femtosecond X-ray pulses provided by X-ray Free Electron Lasers (XFELs) open capabilities for studying the structure and dynamics of a wide variety of biological and inorganic systems beyond what is possible at synchrotron sources. Although the structure and chemistry at the catalytic sites have been studied intensively in both biological and inorganic systems, a full understanding of the atomic-scale chemistry requires new approaches beyond the steady state X-ray crystallography and X-ray spectroscopy at cryogenic temperatures. Following the dynamic changes in the geometric and electronic structure at ambient conditions, while overcoming X-ray damage to the redox active catalytic center, is key for deriving reaction mechanisms. Such studies become possible by using the intense and ultra-short femtosecond X-ray pulses from an XFEL, where sample is probed before it is damaged. We have developed methodology for simultaneously collecting X-ray diffraction data and X-ray emission spectra, using an energy dispersive spectrometer, at ambient conditions, and used this approach to study the room temperature structure and intermediate states of the photosynthetic water oxidizing metallo-protein, photosystem II. Moreover, we have also used this setup to simultaneously collect the X-ray emission spectra from multiple metals to follow the ultrafast dynamics of light-induced charge transfer between multiple metal sites. A Mn-Ti containing system was studied at an XFEL to demonstrate the efficacy and potential of this method.

• 3.
Umeå University, Faculty of Science and Technology, Department of Physics.
Department of Materials Science and Engineering, McMaster University, Hamilton, Ontario, Canada.
Thermal conductivity of Glycerol’s liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures2016In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 144, 064504Article in journal (Refereed)
• 4.
Umeå University, Faculty of Science and Technology, Department of Physics.
Research Center for Structural Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
Thermal Properties and Transition Behavior of Host –Guest Compounds under High Pressure2014In: Current inorganic chemistry, ISSN 1877-9441, Vol. 4, no 1, 2-18 p.Article in journal (Other academic)

The thermal properties and transition behavior of the host-guest inclusion compounds: urea, thiourea, Dianin’s compound, clathrate hydrates and hydroquinone have been reviewed. In particular, we summarize their thermal conductivities, heat capacities and transitions at high pressures. Two of the systems: urea inclusion compounds and clathrate hydrates, show unusual glass-like thermal conductivity k, i.e. their k is low and only weakly dependent on temperature  despite their crystalline structure. Moreover, results for k of Dianin’s compound with guests such as ethanol and CCl4 indicate a change from glass-like k  at atmospheric pressure to crystalline-like k at elevated pressure, whereas k of hydroquinone and thiourea inclusion compounds appears not to have been studied. Despite the technological and fundamental importance of the unusual glass-like k, e.g. the use of inclusion compounds as structural model systems for finding improved thermoelectrical materials, the origin of the glass-like k is not established. More specifically, the commonly employed rattling model, in which rattling guest motions cause resonance scattering of the acoustic host phonons, has recently been challenged, and we discuss alternative models. Heat capacity studies of these compounds reveal numerous transitions, which are associated with guest and host disorder-order transitions upon cooling and pressurization. A transition in hydroquinone may be of second order, or have only a small first-order component, which can explain discrepancies in the observed transition behavior. On pressurization at low temperatures, clathrate hydrates collapse to an amorphous state, which appears to be a glassy state of a water solution with perfectly spaced solute molecules.

• 5. Andrew, Rhiann E.
Coordination Induced Atropisomerism in an NHC-Based Rhodium Macrocycle2015In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 34, no 5, 913-917 p.Article in journal (Refereed)

Reversible interaction with carbon monoxide results in the onset of dynamic atropisomerism at 298 K in an otherwise static NHC-based rhodium pincer complex, [Rh(C boolean AND N boolean AND C-(CH2)(12))(CO)][BArF4] (1, ArF = 3,5-C6H3(CF3)(2)). The mechanism of this process has been comprehensively interrogated by a combination of variable-temperature NMR spectroscopy, IR spectroscopy, and computational modeling. In addition, a structural analogue of a high-energy symmetrical intermediate species-invoked in the process but not directly observed spectroscopically-has been prepared and characterized in solution and the solid-state.

• 6. Arafa, Wael A. A.
Umeå University, Faculty of Science and Technology, Department of Chemistry. Umeå University, Faculty of Science and Technology, Department of Chemistry.
Dinuclear manganese complexes for water oxidation: evaluation of electronic effects and catalytic activity2014In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 16, no 24, 11950-11964 p.Article in journal (Refereed)

During recent years significant progress has been made towards the realization of a sustainable and carbon-neutral energy economy. One promising approach is photochemical splitting of H2O into O-2 and solar fuels, such as H-2. However, the bottleneck in such artificial photosynthetic schemes is the H2O oxidation half reaction where more efficient catalysts are required that lower the kinetic barrier for this process. In particular catalysts based on earth-abundant metals are highly attractive compared to catalysts comprised of noble metals. We have now synthesized a library of dinuclear Mn-2 (II,III) catalysts for H2O oxidation and studied how the incorporation of different substituents affected the electronics and catalytic efficiency. It was found that the incorporation of a distal carboxyl group into the ligand scaffold resulted in a catalyst with increased catalytic activity, most likely because of the fact that the distal group is able to promote proton-coupled electron transfer (PCET) from the high-valent Mn species, thus facilitating O-O bond formation.

MI Lab and Department of Circulation and Medical Imaging, Norwegian University of Science and Technology (NTNU), Trondheim, Norway.
Synthesis and in vitro cellular interactions of superparamagnetic iron nanoparticles with a crystalline gold shell2014In: Applied Surface Science, ISSN 0169-4332, E-ISSN 1873-5584, Vol. 316, 171-178 p.Article in journal (Refereed)

Fe@Au core-shell nanoparticles (NPs) exhibit multiple functionalities enabling their effective use in applications such as medical imaging and drug delivery. In this work, a novel synthetic method was developed and optimized for the synthesis of highly stable, monodisperse Fe@Au NPs of average diameter similar to 24 nm exhibiting magneto-plasmonic characteristics. Fe@Au NPs were characterized by a wide range of experimental techniques, including scanning (transmission) electron microscopy (S(T)EM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS) and UV-vis spectroscopy. The formed particles comprise an amorphous iron core with a crystalline Au shell of tunable thickness, and retain the superparamagnetic properties at room temperature after formation of a crystalline Au shell. After surface modification, PEGylated Fe@Au NPs were used for in vitro studies on olfactory ensheathing cells (OECs) and human neural stem cells (hNSCs). No adverse effects of the Fe@Au particles were observed post-labeling, both cell types retaining normal morphology, viability, proliferation, and motility. It can be concluded that no appreciable toxic effects on both cell types, coupled with multifunctionality and chemical stability make them ideal candidates for therapeutic as well as diagnostic applications.

• 8.
Umeå University, Faculty of Science and Technology, Department of Physics.
Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics.
Palladium nanocrystals supported on photo-transformed C-60 nanorods: effect of crystal morphology and electron mobility on the electrocatalytic activity towards ethanol oxidation2014In: Carbon, ISSN 0008-6223, E-ISSN 1873-3891, Vol. 73, 34-40 p.Article in journal (Refereed)

We report on the synthesis and decoration of high-aspect-ratio crystalline C-60 nanorods (NRs) by functionalized palladium nanoparticles with an average size of 4.78 +/- 0.66 nm. In their pristine form, C-60 NRs suffer from partial damage in the solution-based decoration process resulting in poor crystallinity. However, by modifying the NR surface via in situ photochemical transformation in the liquid state, we are able to prepare highly stable NRs that retain their crystalline structure during the decoration process. Our method thus opens up for the synthesis of highly crystalline nanocomposite hybrids comprising Pd nanoparticles and C-60 NRs. Bys measuring the electron mobility of different C-60 NRs, we relate both the effect of electron mobility and crystallinity to the final electrocatalytic performance of the synthesized hybrid structures. We show that the photo-transformed C-60 NRs exhibit highly advantageous properties for ethanol oxidation based on both a better crystallinity and a higher bulk conductivity. These findings give important information in the search for efficient catalyst support.

• 9.
Umeå University, Faculty of Science and Technology, Department of Physics.
Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics.
Solution-Based Phototransformation of C-60 Nanorods: Towards Improved Electronic Devices2013In: Particle & particle systems characterization, ISSN 0934-0866, E-ISSN 1521-4117, Vol. 30, no 8, 715-720 p.Article in journal (Refereed)

A modified liquid-liquid interface precipitation synthesis of C-60 nanorods, effects and opportunities following an in situ photochemical transformation in the liquid state, and an electronic characterization using a field-effect transistor (FET) geometry are reported. The nanorods feature a high aspect ratio of approximate to 10(3) and a notably small average diameter of 172 nm. Interestingly, it is found that a decreased nanorod diameter appears to correlate with distinctly improved electronic properties, and an average electron mobility of 0.30 cm(2) V-1 s(-1), as measured in a FET geometry, is reported for as-grown nanorods, with the peak value being an impressive 1.0 cm(2) V-1 s(-1). A photoexposure using green laser light ( = 532 nm) is demonstrated to result in the formation of a polymer-C-60 shell encapsulating a monomer-C-60 bulk; such photo-transformed nanorods exhibit an electron mobility of 4.7 x 10(-3) cm(2) V-1 s(-1). It is notable that the utilized FET geometry only probes the polymer-C-60 nanorod surface shell, and that the monomer-C-60 bulk is anticipated to exhibit a higher mobility. Importantly, photoexposed nanorods can be conveniently processed as a stabile dispersion in common hydrophobic solvents, and this finding is attributed to the insoluble character of the polymer-C-60 shell.

• 10.
Umeå University, Faculty of Science and Technology, Department of Chemistry. Industrial Chemistry and Reaction Engineering, Process Chemistry Center (PCC), Department of Chemical Engineering, Åbo Akademi University,Turku/Åbo, Finland.
Umeå University, Faculty of Science and Technology, Department of Chemistry. Industrial Chemistry and Reaction Engineering, Process Chemistry Center (PCC), Department of Chemical Engineering, Åbo Akademi University,Turku/Åbo, Finland.
Application of the Catalyst Wet Pretreatment Method (CWPM) for catalytic direct synthesis of H2O22015In: Catalysis Today, ISSN 0920-5861, E-ISSN 1873-4308, Vol. 246, no Special Issue, 207-215 p.Article in journal (Refereed)

This work concerns a new technique to post-modify the catalytic material intended for use in H2O2 direct synthesis. The catalyst chosen was a commercially available 1 wt.% Pd/C. The catalyst was modified with the so-called Catalyst Wet Pretreatment Method (CWPM) that is used to post-modify prepared catalysts with aqueous solutions of NaBr, in different concentrations. The performance of pristine and the pretreated materials were then compared in the H2O2 direct synthesis and characterized before and after the catalytic tests in order to understand the role of the different concentrations of bromide in the CWPM procedure. The surface features of the different catalysts were analyzed with CO chemisorption (metal dispersion and mean particle size), Transmission Electron Microscopy (TEM, for Pd morphology and Pd particle size distributions), Inductive Coupled Plasma (ICP, for Pd content) and Ion Chromatography (IC, for bromide content). Various features of the materials prepared with the CWPM were correlated with the catalytic performance. It was found that the bromide has an active role in the reconstruction of metal phase and it does not only act as a poison for the most active catalytic sites as often reported in literature. By using this new protocol, the production H2O2 was almost doubled compared to the non-modified material when no direct promoters were added to the reaction environment.

• 11.
Umeå University, Faculty of Science and Technology, Chemistry.
Membrane mediated aggregation of amyloid-β protein: a potential key event in Alzheimer's disease2007Doctoral thesis, comprehensive summary (Other academic)

The pathogenesis of Alzheimer’s disease (AD), the most common senile dementia, is a complex process. A crucial event in AD is the aggregation of amyloid-β protein (Aβ), a cleavage product from the Amyloid Precursor Protein (APP). Aβ40, a common component in amyloid plaques found in patients, aggregates in vitro at concentrations, much higher than the one found in vivo. But in the presence of charged lipid membranes, aggregations occurs at much lower concentration in vitro compared to the membrane-free case. This can be understood due to the ability of Aβ to get electrostatically attracted to target membranes with a pronounced surface potential. This electrostatically driven process accumulates peptide at the membrane surface at concentrations high enough for aggregation while the bulk concentration still remains below threshold. Here, we elucidated the molecular nature of this Aβ-membrane process and its consequences for Aβ misfolding by Circular Dichroism Spectroscopy, Differential Scanning Calorimetry and Nuclear Magnetic Resonance Spectroscopy. First, we revealed by NMR that Aβ40 peptide does indeed interact electrostatically with membranes of negative and positive surface potential. Surprisingly, it even binds to nominal neutral membranes if these contain lipids of opposite charge. Combined NMR and CD studies also revealed that the peptide might be shielded from aggregation when incorporated into the membrane. Moreover, CD studies of Aβ40 added to charged membranes showed that both positively and negatively membranes induce aggregation albeit at different kinetics and finally that macromolecular crowding can both speed up and slow down aggregation of Aβ.

• 12. Cui, Wen
Umeå University, Faculty of Science and Technology, Department of Physics.
Reversible pressure-induced polymerization of Fe(C5H5)(2) doped C-702013In: Carbon, ISSN 0008-6223, E-ISSN 1873-3891, Vol. 62, 447-454 p.Article in journal (Refereed)

High pressure Raman, IR and X-ray diffraction (XRD) studies have been carried out on C-70(Fe(C5H5)(2))(2) (hereafter, "C-70(Fc)(2)") sheets. Theoretical calculation is further used to analyze the Electron Localization Function (ELF) and charge transfer in the crystal and thus to understand the transformation of C-70(Fc)(2) under pressure. Our results show that even at room temperature dimeric phase and one dimensional (1D) polymer phase of C-70 molecules can be formed at about 3 and 8 GPa, respectively. The polymerization is found to be reversible Upon decompression and the reversibility is related to the pressure-tuned charge transfer, as well as the overridden steric repulsion of counter ions. According to the layered structure of the intercalated ferrocene molecules formed in the crystal, we suggest that ferrocene acts as not only a spacer to restrict the polymerization of C-70 molecules within a layer, but also as charge reservoir to tune the polymerization process. This supplies a possible way for us to design the polymerization of fullerenes at suitable conditions.

• 13. da Hora, G. C. A.
Umeå University, Faculty of Science and Technology, Department of Chemistry. Departamento de Quı´mica Fundamental, Universidade Federal de Pernambuco, 50740-560 Cidade Universita´ria, Recife, Brazil.
Membrane negative curvature induced by a hybrid peptide from pediocin PA-1 and plantaricin 149 as revealed by atomistic molecular dynamics simulations2016In: Soft Matter, ISSN 1744-683X, E-ISSN 1744-6848, Vol. 12, no 43, 8884-8898 p.Article in journal (Refereed)

Antimicrobial peptides (AMPs) are cationic peptides that kill bacteria with a broad spectrum of action, low toxicity to mammalian cells and exceptionally low rates of bacterial resistance. These features have led to considerable efforts in developing AMPs as an alternative antibacterial therapy. In vitro studies have shown that AMPs interfere with membrane bilayer integrity via several possible mechanisms, which are not entirely understood. We have performed the synthesis, membrane lysis measurements, and biophysical characterization of a novel hybrid peptide. These measurements show that PA-Pln149 does not form nanopores, but instead promotes membrane rupture. It causes fast rupture of the bacterial model membrane (POPG-rich) at concentrations 100-fold lower than that required for the disruption of mammalian model membranes (POPC-rich). Atomistic molecular dynamics (MD) simulations were performed for single and multiple copies of PA-Pln149 in the presence of mixed and pure POPC/POPG bilayers to investigate the concentration-dependent membrane disruption by the hybrid peptide. These simulations reproduced the experimental trend and provided a potential mechanism of action for PA-Pln149. It shows that the PA-Pln149 does not form nanopores, but instead promotes membrane destabilization through peptide aggregation and induction of membrane negative curvature with the collapse of the lamellar arrangement. The sequence of events depicted for PA-Pln149 may offer insights into the mechanism of action of AMPs previously shown to induce negative deformation of membrane curvature and often associated with peptide translocation via non-bilayer intermediate structures.

• 14. Davidovich, P. B.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Synthesis, structure, biochemical, and docking studies of a new dinitrosyl iron complex [Fe-2(mu-SC4H3SCH2)(2)(NO)(4)]2015In: Journal of Molecular Structure, ISSN 0022-2860, E-ISSN 1872-8014, Vol. 1092, 137-142 p.Article in journal (Refereed)

A new dinitrosyl iron complex of binuclear structure [Fe-2(mu-S-2-methylthiophene)(2)(NO)(4)] was first synthesized and structurally characterized by XRD and theoretical methods. Using caspase-3 as an example it was shown that [Fe-2(mu-S-2-methylthiophene)(2)(NO)(4)] and its analog [Fe-2(mu-S-2-methylfurane)(2)(NO)(4)] can inhibit the action of active site cysteine proteins; the difference in inhibitory activity was explained by molecular docking studies. Biochemical and in silico studies give grounds that the biological activity of dinitrosyl iron complexes is a mu-SR bridging ligand structure function. Thus the rational design strategy of [Fe-2(mu-SR)(2)(NO)(4)] complexes can be applied to make NO prodrugs with high affinity to therapeutically significant targets involved in cancer and inflammation.

• 15.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
NMR-the basic principles and its use in studies of water/ethanol/mixture2012Independent thesis Basic level (degree of Bachelor), 10 credits / 15 HE creditsStudent thesis
• 16. Domashevskaya, EP
Umeå University, Faculty of Science and Technology, Department of Chemistry.
XPS and XANES studies of SnOx nanolayers2008In: Journal of Structural Chemistry, ISSN 0022-4766, E-ISSN 1573-8779, Vol. 49, no Suppl 1, 80-91 p.Article in journal (Refereed)

This paper presents the results of our XPS (X-ray photoelectron spectroscopy) and XANES (X-ray absorption near edge structure) Studies of tin oxide nanolayers obtained by magnetron spraying of the metal and its further oxidation in air at different temperatures. It was shown that at 240 degrees C (annealing temperature), tin monoxide was dominant in the surface layer of the samples. When the temperature was increased to 450 degrees C, the phase composition corresponded to tin dioxide. Increased sorption ability was found for the samples oxidized at 450 degrees C. The band structure model of SnOx nanolayers obtained by superposition of the XANES and XPS data revealed cross transitions with energy similar to 3.7 eV in the presence of the SnO and SnO, phases. Surface doping of nanolayers with palladium gave the Pd, PdO, and PdO2 components, among which PdO was most intense. Alternate treatments with O-2 and H-2 gases led to the disappearance of palladium dioxide and the reduction of PdO to the Pd metal. After the volume doping of nanoplayers with palladium, the surface layer contained PdO and PdO2; the latter was represented by two types of particles with different sizes.

• 17. Drager, Luciano F.
Umeå University, Faculty of Medicine, Department of Medical Biosciences, Physiological chemistry.
Chronic Intermittent Hypoxia Induces Atherosclerosis via Activation of Adipose Angiopoietin-like 42013In: American Journal of Respiratory and Critical Care Medicine, ISSN 1073-449X, E-ISSN 1535-4970, Vol. 188, no 2, 240-248 p.Article in journal (Refereed)

Rationale: Obstructive sleep apnea is a risk factor for dyslipidemia and atherosclerosis, which have been attributed to chronic intermittent hypoxia (CIH). Intermittent hypoxia inhibits a key enzyme of lipoprotein clearance, lipoprotein lipase, and up-regulates a lipoprotein lipase inhibitor, angiopoietin-like 4 (Angptl4), in adipose tissue. The effects and mechanisms of Angptl4 up-regulation in sleep apnea are unknown. Objectives: To examine whether CIH induces dyslipidemia and atherosclerosis by increasing adipose Angptl4 via hypoxia-inducible factor-1 (HIF-1). Methods: ApoE(-/-) mice were exposed to intermittent hypoxia or air for 4 weeks while being treated with Angptl4-neutralizing antibody or vehicle. Measurements and Main Results: In vehicle-treated mice, hypoxia increased adipose Angptl4 levels, inhibited adipose lipoprotein lipase, increased fasting levels of plasma triglycerides and very low density lipoprotein cholesterol, and increased the size of atherosclerotic plaques. The effects of CIH were abolished by the antibody. Hypoxia-induced increases in plasma fasting triglycerides and adipose Angptl4 were not observed in mice with germline heterozygosity for a HIF-1 alpha knockout allele. Transgenic overexpression of HIF-1 alpha in adipose tissue led to dyslipidemia and increased levels of adipose Angptl4. In cultured adipocytes, constitutive expression of HIF-1 alpha increased Angptl4 levels, which was abolished by siRNA. Finally, in obese patients undergoing bariatric surgery, the severity of nocturnal hypoxemia predicted Angptl4 levels in subcutaneous adipose tissue. Conclusions: HIF-1-mediated increase in adipose Angptl4 and the ensuing lipoprotein lipase in activation may contribute to atherosclerosis in patients with sleep apnea.

• 18.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Chemistry. Umeå University, Faculty of Science and Technology, Department of Chemistry. 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, 4975-4988 p.Article in journal (Refereed)

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.

• 19. Du, Mingrun
Umeå University, Faculty of Science and Technology, Department of Physics. State Key Laboratory of Superhard Materials, Jilin University, Changchun, PR China.
High pressure infrared spectroscopy study on C60*CS2 solvates2017In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 669, 49-53 p.Article in journal (Refereed)

High pressure IR study has been carried out on C-60*CS2 solvates up to 34.8 GPa. It is found that the intercalated CS2 molecules significantly affect the transformations of C-60 molecules under pressure. As a probe, the intercalated CS2 molecules can well detect the orientational ordering transition and deformation of C-60 molecules under pressure. The chemical stability of CS2 molecules under pressure is also dramatically enhanced due to the spacial shielding effet from C-60 molecules around in the solvated crystal. These results provide new insight into the effect of interactions between intercalants and fullerenes on the transformations in fullerene solvates under pressure.

The full text will be freely available from 2019-02-28 09:36
• 20. Dyson, P J
Determination of hydrogen concentration in ionic liquids and the effect (or lack of) on rates of hydrogenation2003In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, no 19, 2418-2419 p.Article in journal (Refereed)

The solubility of hydrogen and the corresponding Henry coefficients for 11 ionic liquids have been determined in situ at 100 atm H(2) pressure and are much lower than expected; attempts to correlate the solubility of hydrogen in the ionic liquids with the rate of reaction for the hydrogenation of benzene to cyclohexane in these solvents have been made.

• 21.
Umeå University, Faculty of Science and Technology, Department of Physics.
Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics.
Facile fabrication of efficient organic CMOS circuits2010In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 114, no 1, 135-140 p.Article in journal (Refereed)

Organic electronic circuits based on a combination of n- and p-type transistors (so-called CMOS circuits) are attractive, since they promise the realization of a manifold of versatile and low-cost electronic devices. Here, we report a novel photoinduced transformation method, which allows for a particularly straightforward fabrication of highly functional organic CMOS circuits. A solution-deposited single-layer film, comprising a mixture of the n-type semiconductor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and the p-type semiconductor poly-3-hexylthiophene (P3HT) in a 3:1 mass ratio, was utilized as the common active material in an array of transistors. Selected film areas were exposed to laser light, with the result that the irradiated PCBM monomers were photochemically transformed into a low-solubility and high-mobility dimeric state. Thereafter, the entire film was developed via immersion into a developer solution, which selectively removed the nonexposed, and monomeric, PCBM component. The end result was that the transistors in the exposed film areas are n-type, as dimeric PCBM is the majority component in the active material, while the transistors in the nonexposed film areas are p-type, as P3HT is the sole remaining material. We demonstrate the merit of the method by utilizing the resulting combination of n-type and p-type transistors for the realization of CMOS inverters with a high gain of ∼35.

• 22.
Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics.
Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics.
ICL-based TDLAS sensor for real-time breath gas analysis of carbon monoxide isotopes2017In: Optics Express, ISSN 1094-4087, E-ISSN 1094-4087, Vol. 25, no 11, 12743-12752 p.Article in journal (Refereed)

We present a compact sensor for carbon monoxide (CO) in air and exhaled breath based on a room temperature interband cascade laser (ICL) operating at 4.69 µm, a low-volume circular multipass cell and wavelength modulation absorption spectroscopy. A fringe-limited (1σ) sensitivity of 6.5 × 10−8 cm−1Hz-1/2 and a detection limit of 9 ± 5 ppbv at 0.07 s acquisition time are achieved, which constitutes a 25-fold improvement compared to direct absorption spectroscopy. Integration over 10 s increases the precision to 0.6 ppbv. The setup also allows measuring the stable isotope 13CO in breath. We demonstrate quantification of indoor air CO and real-time detection of CO expirograms from healthy non-smokers and a healthy smoker before and after smoking. Isotope ratio analysis indicates depletion of 13CO in breath compared to natural abundance.

• 23. Gorkina, Alexandra L
Umeå University, Faculty of Science and Technology, Department of Physics.
Transparent and conductive hybrid graphene/carbon nanotube films2016In: Carbon, ISSN 0008-6223, E-ISSN 1873-3891, Vol. 100, 501-507 p.Article in journal (Refereed)

Carbon nanomaterials (carbon nanotubes (CNTs) and graphene) are promising materials for optoelectronic applications, including flexible transparent and conductive films (TCFs) due to their extraordinary electrical, optical and mechanical properties. However, the performance of CNT- or graphene-only TCFs still needs to be improved. One way to enhance the optoelectrical properties of TCFs is to hybridize CNTs and graphene. This approach leads to creation of a novel material that exhibits better properties than its individual constituents. In this work, the novel hybrid CNT-graphene nanomaterial was fabricated by graphene oxide deposition on top of CNT films. The graphene oxide was then reduced by thermal annealing at ambient atmosphere or in H2 atmosphere. At the final step the CNT-graphene hybrids were chemically doped using gold(III) chloride. As a result, we show that the hybrids demonstrate excellent optoelectrical performance with the sheet resistance as low as 73 Ω/□ at 90% transmittance.

• 24.
Umeå University, Faculty of Science and Technology, Department of Physics.
Behind the Synergistic Effect Observed on Phosphorus Nitrogen Codoped Graphene during the Oxygen Reduction Reaction2016In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 49, 27849-27857 p.Article in journal (Refereed)

Ab initio calculations are performed to investigate how the simultaneous introduction of phosphorus and nitrogen into graphene modifies the availability and spatial distribution of catalytic active sites for an oxygen reduction reaction (ORR). A phosphoryl group (R-3-P=0) is selected as a representative for the phosphorus doping, and the ORR is studied under alkaline conditions where a 4e(-) mechanism is used to determine the limiting step and overpotential (eta(ORR)) along the entire graphene surface. A scanning procedure is used to construct eta(ORR) maps for pristine-, N-, P-, and diverse PN codoped graphenes. The results indicate that a single N (P) atom activates up to 17 (3) C atoms, while the simultaneous introduction of P and N activates up to 55 C atoms equivalent to 57% of the surface. Additionally, PN codoped graphenes reveals that the relative location of both dopants has significant effects on the ORR performance, where a P N separation distance of at least 4 angstrom minimizes the localization of electronic states on the neighboring C atoms and improves the quantity and distribution of active sites. The results shows the importance of designing synthesis procedures to control the dopant concentration and spatial distribution to maximize the number of active sites. Furthermore, the eta(ORR) maps reveal features that could be obtained by scanning tunneling microscopy allowing us to experimentally identify and possibly quantify the catalytic active sites on carbon-based materials.

• 25.
Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics.
Fabrication of One-Dimensional Zigzag [6,6]-Phenyl-C-61-Butyric Acid Methyl Ester Nanoribbons from Two-Dimensional Nanosheets2015In: ACS Nano, ISSN 1936-0851, E-ISSN 1936-086X, Vol. 9, no 10, 10516-10522 p.Article in journal (Refereed)

One-dimensional (10) zigzag [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) nanoribbons are produced by folding two-dimensional ultrathin PCBM nanosheets in a simple solvent process. The unique 1D PCBM nanostructures exhibit uniform width of 3.8 +/- 0.3 nm, equivalent to four PCBM molecules, and lengths of 20-400 nm. These nanoribbons show well-defined crystalline structure, comprising PCBM molecules in a hexagonal arrangement without trapped solvent molecules. First-principle calculations and detailed experimental characterization provide an insight into the structure and formation mechanism of the 1D PCBM nanoribbons. Given their dimensions and physical properties, we foresee that these nanostructures should be ideal as acceptor material in organic solar cells.

• 26.
Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Chemistry. Advanced Materials Department, IPICYT, México.
Self-assembly synthesis of decorated nitrogen-doped carbon nanotubes with ZnO nanoparticles: anchoring mechanism and the effects of sulfur2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 1, 741-747 p.Article in journal (Refereed)

Hybrid systems consisting of ZnO nanoparticles (ZnO-NPs) anchored on the surface of nitrogen-doped multiwalled carbon nanotubes (CNX-MWNTs) have been synthesized. The anchoring process consists of a self-assembly method involving the mixing of CNX-MWNTs in a solution with N,N-dimethylformamide, zinc acetylacetonate, and thiophene. Thiophene is used as a capping agent for controlling the size and distribution of ZnO-NPs, as well as an anchoring element between the NPs and the nanotube walls. Scanning and transmission electron microscopy characterization revealed that the ZnO-NPs are homogeneously deposited on the surface of CNX-MWNTs. X-ray powder diffraction analysis demonstrated that the ZnO-NPs exhibit a Wurtzite-type crystal structure with an average particle diameter of 5 nm. We also show that the ZnO-NPs do not exhibit a preferential growth direction with respect to the nanotube surface, and their formation is simply controlled by the concentration of the passivating agent. Density functional theory (DFT) calculations confirm that sulfur (from thiophene) is an effective passivating agent for ZnO by preferentially binding low-coordinated Zn atoms. However, the ZnO-NPs could be chemically bonded to the nanotubes through oxygen atoms close to the nitrogenated sites of the tubes. Our results also demonstrate that isolated and sulfur passivated ZnO-NPs become magnetic and exhibit half-metallicity (electronic states with only one spin component are present at the Fermi level). Sulfur-passivated ZnO retains these properties even after forming ZnO/CNX-MWNT hybrid materials.

• 27. Harley, Steven J.
Geochemical kinetics via the Swift-Connick equations and solution NMR2011In: Geochimica et Cosmochimica Acta, ISSN 0016-7037, E-ISSN 1872-9533, Vol. 75, no 13, 3711-3725 p.Article in journal (Refereed)

Signal analysis in Nuclear Magnetic Resonance spectroscopy is among the most powerful methods to quantify reaction rates in aqueous solutions. To this end, the Swift-Connick approximations to the Bloch-McConnell equations have been used extensively to estimate rate parameters for elementary reactions. The method is primarily used for O-17 NMR in aqueous solutions, but the list of geochemically relevant nuclei that can be used is long, and includes Si-29, Al-27, F-19, C-13 and many others of particular interest to geochemists. Here we review the derivation of both the Swift-Connick and Bloch-McConnell equations and emphasize assumptions and quirks. For example, the equations were derived for CW-NMR, but are used with modern pulse FT-NMR and can be applied to systems that have exchange rates that are shorter than the lifetime of a typical pulse. The method requires a dilute solution where the minor reacting species contributes a negligible amount of total magnetization. We evaluate the sensitivity of results to this dilute-solution requirement and also highlight the need for chemically well-defined systems if reliable data are to be obtained. The limitations in using longitudinal relaxation to estimate reaction rate parameters are discussed. Finally, we provide examples of the application of the method, including ligand exchanges from aqua ions and hydrolysis complexes, that emphasize its flexibility. Once the basic requirements of the Swift-Connick method are met, it allows geochemists to establish rates of elementary reactions. Reactions at this scale lend themselves well to methods of computational simulation and could provide key tests of accuracy. (C) 2011 Elsevier Ltd. All rights reserved.

• 28. Harley, Steven J.
The Pressure Dependence of Oxygen Isotope Exchange Rates Between Solution and Apical Oxygen Atoms on the [UO2(OH)(4)](2-) Ion2011In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 50, no 19, 4467-4469 p.Article in journal (Refereed)
• 29. He, Hanbing
Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics. Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics.
Mechanism of Quartz Bed Particle Layer Formation in Fluidized Bed Combustion of Wood-Derived Fuels2016In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 30, no 3, 2227-2232 p.Article in journal (Refereed)

Agglomeration is among one of the major problems in the operation of fluidized bed boilers. The formation of bed particle layers is thought to play an important role on the occurrence of agglomeration in wood-fired fluidized (quartz) beds. In spite of frequent experimental reports on the quartz bed particle layer characteristics, the underlying bed layer formation process has not yet been presented. By combining our previously experimental results on layer characteristics for samples with durations from 4 h to 23 days, with phase diagrams, thermochemical equilibrium calculations, and a diffusion model, a mechanism of quartz bed particle layer formation was proposed. For younger bed particles (<around 1 day), the layer growth process is accelerated due to a high diffusion of calcium in a K-rich silicate melt. However, with continuous addition of calcium into the layer, the amount of melt decreases and crystalline Ca-silicates starts to form. Ca2SiO4 is the dominating crystalline phase in the inner layer, while the formation of CaSiO3 and possibly Ca3SiO5 are favored for younger and older bed particles, respectively. The decreasing amount of melt and formation of crystalline phases result in low diffusion rates of calcium in the inner layer and the layer growth process becomes diffusion controlled after around 1 day.

• 30.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Chemistry.
Characterization of Hydrogenated Fullerenes by NMR Spectroscopy2010In: Fulleranes: The Hydrogenated Fullerenes / [ed] Franco Cataldo, Susana Iglesias-Groth, Dordrecht: Springer Netherlands, 2010, Vol. 2, 171-202 p.Chapter in book (Other academic)

NMR spectroscopy is so far the only analytical technique that has been used to get a detailed structural characterization of hydrogenated fullerenes. A substantial amount of information derived from different NMR experiments can thus be found in the literature for a number of fullerenes hydrogenated to various degrees. These studies have benefitted from the fact that chemical shifts of H-1 and C-13 and in some cases also He-3 can be used to obtain structural information of these compounds. Such results, together with discussions about different NMR experiments and general considerations regarding sample preparations, are summarized in this chapter. The unique information, both structural and physicochemical, that can be derived from different NMR experiments ensures that this technique will continue to be of central importance in characterization of hydrogenated fullerenes.

• 31.
Umeå University, Faculty of Science and Technology, Department of Physics. Laboratory of Environmental Science and Technology, The Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830011, China.
Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics. Umeå University, Faculty of Science and Technology, Department of Physics.
Atomistic understanding of the origin of high oxygen reduction electrocatalytic activity of cuboctahedral Pt3Co-Pt core-shell nanoparticles2016In: Catalysis Science & Technology, ISSN 2044-4753, E-ISSN 2044-4761, Vol. 6, no 5, 1393-1401 p.Article in journal (Refereed)

PtM-based core-shell nanoparticles are a new class of active and stable nanocatalysts for promoting oxygen reduction reaction (ORR); however, the understanding of their high electrocatalytic performance for ORR at the atomistic level is still a great challenge. Herein, we report the synthesis of highly ordered and homogeneous truncated cuboctahedral Pt3Co-Pt core-shell nanoparticles (cs-Pt3Co). By combining atomic resolution electron microscopy, X-ray photoelectron spectroscopy, extensive first-principles calculations, and many other characterization techniques, we conclude that the cs-Pt3Co nanoparticles are composed of a complete or nearly complete Pt monolayer skin, followed by a secondary shell containing 5-6 layers with similar to 78 at% of Pt, in a Pt3Co configuration, and finally a Co-rich core with 64 at% of Pt. Only this particular structure is consistent with the very high electrocatalytic activity of cs-Pt3Co nanoparticles for ORR, which is about 6 times higher than commercial 30%-Pt/Vulcan and 5 times more active than non-faceted (spherical) alloy Pt3Co nanoparticles. Our study gives an important insight into the atomistic design and understanding of advanced bimetallic nanoparticles for ORR catalysis and other important industrial catalytic applications.

• 32.
J. Heyrovský Institute of Physical Chemistry, Prague, Czech Republic.
J. Heyrovský Institute of Physical Chemistry, Prague, Czech Republic. J. Heyrovský Institute of Physical Chemistry, Prague, Czech Republic. J. Heyrovský Institute of Physical Chemistry, Prague, Czech Republic. J. Heyrovský Institute of Physical Chemistry, Prague, Czech Republic. Umeå University, Faculty of Science and Technology, Department of Chemistry. J. Heyrovský Institute of Physical Chemistry, Prague, Czech Republic.
Dynamics and size of crosslinking-induced lipid nanodomains in model membranes2012In: Biophysical Journal, ISSN 0006-3495, E-ISSN 1542-0086, Vol. 102, no 3, 294a- p.Article in journal (Refereed)

Changes of membrane organization upon crosslinking of its components trigger cellsignaling response to various exogenous factors. Crosslinking of raft gangliosides GM1with cholera toxin (CTxB) was demonstrated to cause microscopic phase separation inmodel membranes and the CTxB-GM1 complexes forming a minimal lipid raft unit aresubject of ongoing cell membrane research. Yet, those subdiffraction sized rafts havenever been described in terms of size and dynamics. By means of two-color z-scanfluorescence correlation spectroscopy, we show that the nano-sized domains are formedin model membranes at lower sphingomyelin content than needed for the large scalephase separation and that the CTxB-GM1 complexes are confined in the domains poorlystabilized with sphingomyelin. Fluorescence resonance energy transfer together withMonte Carlo modeling of the donor decay response reveal the domain radius ofapproximately 8 nm, which increases at higher sphingomyelin content. We observed twotypes of differently behaving domains, which suggests a dual role of the crosslinker: first,local transient condensation of the GM1 molecules compensating lack of sphingomyelinand second, coalescence of existing nanodomains ending in large scale phase separation.

• 33.
Umeå University, Faculty of Science and Technology, Chemistry.
Simulation of Relaxation Processes in Fluorescence, EPR and NMR Spectroscopy2004Doctoral thesis, comprehensive summary (Other academic)

Relaxation models are developed using numerical solutions of the Stochastic Liouville Equation of motion. Simplified descriptions such as the stochastic master equation is described in the context of fluorescence depolarisation experiments. Redfield theory is used in order to describe NMR relaxation in bicontinuous phases. The stochastic fluctuations in the relaxation models are accounted for using Brownian Dynamics simulation technique. A novel approach to quantitatively analyse fluorescence depolarisation experiments and to determine intramolecular distances is presented. A new Brownian Dynamics simulation technique is developed in order to characterize translational diffusion along the water lipid interface of bicontinuous cubic phases.

Umeå University, Faculty of Science and Technology, Department of Chemistry.
Benchmark study of UV/Visible spectra of coumarin derivatives by computational approach2017In: Journal of Molecular Structure, ISSN 0022-2860, E-ISSN 1872-8014, Vol. 1130, 603-616 p.Article in journal (Refereed)

A benchmark study of UV/Visible spectra of Simple coumarins and Furanocoumarins derivatives was conducted by employing the Density Functional Theory (DFT) and Time Dependent Density Functional Theory (TD-DFT) approaches. In this study the geometries of ground and excited states, excitation energy and absorption spectra were estimated by using the DFT functional CAM-B3LYP, WB97XD, HSEH1PBE, MPW1PW91 and TD-B3LYP with 6-31 + G (d,p) basis set. CAM-B3LYP functional was found to have close agreement with the experimental values of Furranocoumarin class of coumarins while MPW1PW91 gave close results for simple coumarins. This study provided an insight about the electronic characteristics of the selected compounds and provided an effective tool for developing and designing the better UV absorber compounds.

• 35.
Umeå University, Faculty of Science and Technology, Chemistry.
On the quantitative analysis of electronic energy transfer/migration in proteins studied by fluorescence spectroscopy2007Doctoral thesis, comprehensive summary (Other academic)

Two recently developed theories of electronic energy transfer/migration were for the first time applied to real protein systems for extracting molecular distances. The partial donor-donor energy migration (PDDEM) is an extension to the previously developed donor-donor energy migration (DDEM, F Bergström et al PNAS 96, 1999, 12477) which allows using chemically identical but photophysically different fluorophores in energy migration experiments. A method based on fluorescence quenching was investigated and applied to create an asymmetric energy migration between fluorophores which were covalently and specifically attached to plasminogen activator inhibitor type 2 (PAI-2). It was also shown experimentally that distance information can be obtained if the fluorescence relaxation for photophysically identical donors, exhibits multi-exponential relaxation.

An extended Förster theory (EFT) that was previously derived (L. B.-Å. Johansson et al J. Chem. Phys., 1996, 105) ha been developed for analysis of donor-acceptor energy transfer systems as well as DDEM systems. Recently the EFT was also applied to determine intra molecular distances in the protein plasminogen activator inhibitor type 1 (PAI-1) which was labelled with a sulfhydryl specific derivative of BODIPY. The EFT explicitly accounts for the time-dependent reorientations which in a complex manner influence the rate of electronic energy transfer/migration. This difficulty is related to the “k2-problem”, which has been solved. It is also shown experimentally that the time-correlated single-photon counting (TCSPC) data is sensitive to the mutual configuration between the interacting fluorophores. To increase the accuracy in the extracted parameters it is furthermore suggested to collect the fluorescence data under various physico-chemical conditions. It was also shown that the Förster theory is only valid in the initial part of the fluorescence decay.

• 36. Jogunola, Olatunde
Umeå University, Faculty of Science and Technology, Department of Chemistry. Åbo Akademi, Johan Gadolin Process Chemistry Centre, Laboratory of Industrial Chemistry and Reaction Engineering, Åbo/Turku, Finland.
Complexation equilibria studies of alkyl formate hydrolysis in the presence of 1-butylimidazole2017In: Thermochimica Acta, ISSN 0040-6031, E-ISSN 1872-762X, Vol. 652, 62-68 p.Article in journal (Refereed)

Formic acid production by ethyl or methyl formate hydrolysis was improved using 1-butylimidazole as a complexing agent. The chemical process involved both hydrolysis and complexation steps. The complexation equilibria were investigated by deriving theoretical equations using the equilibrium constant of the hydrolysis step, the apparent formation constant of the complexation process and the initial concentration of the complexing agent. The treatment of the experimental results within the experimental domain indicated that an equimolar amount of the acid and the base did not lead to the complex formation. Experimental observation suggested that the derived equation could be simplified by assuming that the stoichiometric coefficient of the complexing agent was 0.5. The apparent reaction enthalpy obtained from this equation was compared to the experimental one using a Tian-Calvet calorimeter and a good agreement was found between them. FTIR spectroscopy was used to confirm the existence of the complex between formic acid and 1-butylimidazole.

• 37. Johari, G. P.
Umeå University, Faculty of Science and Technology, Department of Physics.
Structural relaxation and thermal conductivity of high-pressure formed, high-density di-n-butyl phthalate glass and pressure induced departures from equilibrium state2017In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 146, no 23, 234505Article in journal (Refereed)

We report a study of structural relaxation of high-density glasses of di-n-butyl phthalate (DBP) by measuring thermal conductivity, κ, under conditions of pressure and temperature (p,T) designed to modify both the vibrational and configurational states of a glass. Various high-density glassy states of DBP were formed by (i) cooling the liquid under a fixed high p and partially depressurizing the glass, (ii) isothermal annealing of the depressurized glass, and (iii) pressurizing the glass formed by cooling the liquid under low p. At a given low p, κ of the glass formed by cooling under high p is higher than that of the glass formed by cooling under low p, and the difference increases as glass formation p is increased. κ of the glass formed under 1 GPa is ∼20% higher at ambient p than κ of the glass formed at ambient p. On heating at low p, κ decreases until the glass to liquid transition range is reached. This is the opposite of the increase in κ observed when a glass formed under a certain p is heated under the same p. At a given high p, κ of the low-density glass formed by cooling at low p is lower than that of the high-density glass formed by cooling at that high p. On heating at high p, κ increases until the glass to liquid transition range is reached. The effects observed are due to a thermally assisted approach toward equilibrium at p different from the glass formation p. In all cases, the density, enthalpy, and entropy would change until the glasses become metastable liquids at a fixed p, thus qualitatively relating κ to variation in these properties.

• 38. Johnson, Rene L.
Multinuclear NMR Study of the Pressure Dependence for Carbonate Exchange in the UO2(CO3)34-(aq) Ion2011In: ChemPhysChem, ISSN 1439-4235, E-ISSN 1439-7641, Vol. 12, no 16, 2903-2906 p.Article in journal (Refereed)
• 39. Johnson, Rene L.
Dynamics of a Nanometer-Sized Uranyl Cluster in Solution2013In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 52, no 29, 7464-7467 p.Article in journal (Refereed)
• 40. Johnson, Rene L.
O-17 NMR and Computational Study of a Tetrasiliconiobate Ion, [H2+xSi4Nb16O56]((14-x)-)2011In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 17, no 34, 9359-9367 p.Article in journal (Refereed)

Rates of oxygen-isotope exchange were measured in the tetrasiliconiobate ion [H2+xSi4Nb16O56]((14-x)-) to better understand how large oxide ions interact with water. The molecule has 19 nonequivalent oxygen sites and is sufficiently complex to evaluate hypotheses derived from our previous work on smaller clusters. We want to examine the extent to which individual oxygen atoms react independently with particular attention given to the order of protonation of the various oxygen sites as the pH decreases from 13 to 6. As in our previous work, we find that the set of oxygen sites reacts at rates that vary over approximately 104 across the molecule at 6 < pH < 13 but with similar pH dependencies. There is NMR evidence of an intra-or intermolecular reaction at pH similar to 7, where new peaks began to slowly form without losing the O-17 isotopic tag, and at pH <= 6 these new peaks formed rapidly. The oxygen atoms bonded to silicon atoms began to isotopically exchange at pH 9 and below. The 17O NMR peak positions also vary considerably with pH for some, but not all, nonequivalent oxygen sites. This variation could be only partly accounted by electronic calculations, which indicate that oxygen atoms should shift similarly upon protonation. Instead, we see that some sites change enormously with pH, whereas other, similarly coordinated oxygen atoms are less affected, suggesting that either some protons are exchanging so rapidly that the oxygen sites are seeing an averaged charge, or that counterions are modulating the effect of the coordinated protons.

• 41.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Electronic Energy Transfer within Asymmetric Pairs of Fluorophores: Partial Donor-Donor Energy Migration (PDDEM)2004Doctoral thesis, comprehensive summary (Other academic)

A kinetic model of electronic energy migration within pairs of photophysically non-identical fluorophores has been developed. The model applies to fluorescent groups that exhibit different photophysical and spectral properties when attached to different positions in a macromolecule. The energy migration within such asymmetric pairs is partially reversible, which leads to the case of partial donor-donor energy migration (PDDEM). The model of PDDEM is an extension of the recently developed donor-donor energy migration model (DDEM, F. Bergström et al, PNAS 96 (1999) 12477), and applies to quantitative measurements of energy migration rates and distances within macromolecules. One important distinction from the DDEM model is that the distances can be obtained from fluorescence lifetime measurements. A model of fluorescence depolarisation in the presence of PDDEM is also presented.

To experimentally test the PDDEM approach, different model systems were studied. The model was applied to measure distances between rhodamine and fluorescein groups within on-purpose synthesised molecules that were solubilised in lipid bilayers. Moreover, distances were measured between BODIPY groups in mutant forms of the plasminogen activator inhibitor of type 2 (PAI-2). Measurements of both the fluorescence intensity decays and the time-resolved depolarisation were performed. The obtained distances were in good agreement with independent determinations.

Finally, the PDDEM within pairs of donors is considered, for which both donors exhibit a nonexponential fluorescence decay. In this case it turns out that the fluorescence relaxation of a coupled system contains distance information even if the photophysics of the donors is identical. It is also demonstrated that the choice of relaxation model has a negligible effect on the obtained distances. The latter conclusion holds also for the case of donor-acceptor energy transfer.

Umeå University, Faculty of Medicine, Department of Integrative Medical Biology (IMB).
Influence of the alkyl side-chain length on the ultrafast vibrational dynamics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide (C(n)mimNTf(2)) ionic liquids2017In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 19, no 24, 15988-15995 p.Article in journal (Refereed)

Probing the vibrational dynamics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (CnmimNTf2) ionic liquids (ILs) using femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) has indicated the ultrafast vibrational energy transfer between counter ions which is governed by interionic interactions and facilitated by hydrogen bonds. In this study, fs-CARS is used to investigate the ultrafast dynamics of the vibrational modes of the CnmimNTf2 ILs with n = 6, 8, 10, and 12 in a spectral region, which involves the imidazolium ring and the alkyl side-chain vibrations. The vibrational Raman modes with wavenumbers around 1418 cm−1 are excited through the CARS process and the ultrafast time evolution of the consequently excited vibrational modes is monitored. The investigation of the life times of the fs-CARS transient signals indicates that the time scale of the dynamics becomes much faster when the alkyl side-chain length of the CnmimNTf2 is longer than n = 8. This observation suggests an increase in the hydrogen bonding interactions due to the nano-structuring of the ionic liquids, which became evident with an increasing length of the alkyl side-chain. This behavior is also found in molecular dynamics simulations. There, an increase of the oxygen density around the C(2)–H moiety of the imidazolium ring, which is the predominant site for hydrogen bond formation, is observed. In other words, the longer the alkyl side-chain, the more reorganization of the ionic liquid into polar and non-polar domains occurs and the higher the probability of finding interionic hydrogen bonds at the C(2)–H position becomes.

• 43.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Electrochemical investigations on lipid cubic phases2017Doctoral thesis, comprehensive summary (Other academic)

Electrochemical Impedance Spectroscopy (EIS) was used to develop a novel methodology for studying ionic interaction with lipids arranged in a lipid cubic phase (LCP). Studying different types of ions, both cations and anions, validated the method. A free-standing LCP membrane was formed between two cell compartments and impedance experiments were carried out in a 2-electrode setup to estimate dielectric properties of the membrane, exposed to the following electrolyte solutions at different concentrations: KCl, CsBr, CaCl2, MgCl2, CsCl, NaCl, NaOAc and NaTryptophan. Two different LCP were used in this setup, i.e: Monoloein/water and the ternary system of monoolein/dioleoylphosphatidylcholine/water (MO/DOPC/H2O). SAXRD measurements were performed to determine the space group of the cubic phase and confirm the stability of the LCP during measurements.

Membrane resistances and capacitances were found from equivalent circuit fitting to the impedance data. The membrane resistance was shown to be related to ionic interaction with the lipid head group in the water channels of the LCP. Membrane capacitance were correlating to condensing and swelling effect of LCP due to the exposure of ions. The results correlated well with the SAXRD results and earlier published data.

The results also indicate that these membranes become less permeable to ions as they increase in size as well as in charge or polarity.

Cyclic voltammetry was used to study the applications of a LCP for modification of the bioanode in a biofuel cell. The monoolein cubic phase was used to host Glucose oxidase (GOx) and a freely diffusing ferrocene carboxylate was used as mediator. The supported cubic phase had an intrinsic resistance in the same order of magnitude as the freestanding MO-LCP membrane as measured with EIS.

• 44.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Photophysical and DFT Characterization of Novel Pt(II)-Coupled 2,5-Diaryloxazoles for Nonlinear Optical Absorption2012In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 116, no 47, 11519-11530 p.Article in journal (Refereed)

Several new bis-phosphine platinum(II) complexes with 2,5-diaryl-substituted oxazole-containing alkyne ligands have been synthesized and optically characterized in solution. Measurements of nonlinear absorption showed strong attenuation of laser light at 532 and 600 nm. The light absorption of the Pt complexes was shifted from the near-UV region for the ground state to the red region for the excited triplet state, and was associated with large extinction coefficients. The optical limiting effect can be explained by triplet-triplet excited state absorption in conjunction with fast excited singlet to-triplet intersystem crossing and slow triplet to-ground-state decay, in comparison with the pulse length of the laser. DFT calculations show good predictability of the S-0-S-1 and S-0-T-1 energy gaps and offer insight into the interaction strength between Pt and the alkyne ligands. The use of this type of ligand, with weak absorption for the Pt(II) complexes in the visual wavelength range as a key feature, enables the possibility to further improve these molecular systems for nonlinear absorption applications.

• 45. Kirilin, A
Umeå University, Faculty of Science and Technology, Department of Chemistry. Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics. Umeå University, Faculty of Science and Technology, Department of Chemistry. Process Chemistry Centre, Laboratory of Industrial Chemistry and Reaction Engineering, Åbo Akademi University, Turku/Åbo, Finland .
Chemo-Bio Catalyzed Synthesis of R-1-Phenylethyl Acetate over Bimetallic PdZn Catalysts, Lipase, and Ru/Al2O3: part II2011In: Kinetics and catalysis, ISSN 0023-1584, E-ISSN 1608-3210, Vol. 52, no 1, 77-81 p.Article in journal (Refereed)

One-pot synthesis of R-1-phenyethylacetate at 70 degrees C was investigated using three different catalysts simultaneously, namely a bimetallic PdZn/Al2O3 as a hydrogenation catalyst, an immobilized lipase as an acylation catalyst and Ru/Al2O3 as a racemization catalyst. The most active bimetallic catalyst was PdZn/Al2O3 calcined at 300 degrees C and reduced at 400 degrees C, whereas the most selective although less active catalyst was the one being calcined and reduced at 500 degrees C. The highest selectivity to R-1-phenylethyl acetate over this catalyst was 32 at 48% conversion. Ru/Al2O3 was confirmed to have a positive effect on the formation of the desired product, although it was not very active in the racemization during one-pot synthesis.

• 46. Kirilin, A
Umeå University, Faculty of Science and Technology, Department of Chemistry. Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics, Energy Technology and Thermal Process Chemistry. Umeå University, Faculty of Science and Technology, Department of Chemistry.
Chemo-bio catalyzed synthesis of R-1-phenylethyl acetateover bimetallic PdZn catalysts, lipase and Ru/Al2o3. Part I2011In: Kinetics and catalysis, ISSN 0023-1584, E-ISSN 1608-3210, Vol. 52, no 1, 72-76 p.Article in journal (Refereed)

The effect of calcination and reduction temperature on the physical properties of PdZn/Al2O3 catalysts, prepared by coprecipitation deposition technique and characterized by XPS, XRD and TEM methods are reported. The temperatures were varied in a range of 300–500°C. The catalyst calcined at 300°C and reducedat 400°C exhibited the metal particle size of 2–6 nm and contained the highest surface concentrations of Pd and Zn according to XPS measurements. The size and the fraction of large particles (above 10 nm) increased with increasing the calcinations and reduction temperatures.

• 47. Konwar, Lakhya Jyoti
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Towards carbon efficient biorefining: Multifunctional mesoporous solid acids obtained from biodiesel production wastes for biomass conversion2015In: Applied Catalysis B: Environmental, ISSN 0926-3373, E-ISSN 1873-3883, Vol. 176, 20-35 p.Article in journal (Refereed)

Multifunctional mesoporous solid acids were prepared by the sulfonation of carbonized de-oiled seed waste cake (DOWC), a solid waste from biodiesel production. Detailed structural characterization of the materials by elemental analysis, FT-IR, Raman, XRD, XPS, TGA, NH3-TPD and N-2-physisorption showed that they were structurally different from the carbohydrate and resin based sulfonated carbon catalysts. In addition to the typical -OH, -COOH and -SO3H groups they contain several N species (pyridinic, pyrrolic etc.) incorporated in their carbon frameworks. The basic structural unit of these materials is a flexible carbon nitride sheet which is extensively functionalized with acidic groups. Our results show distinct effects of raw material composition and preparation methods (activation, sulfonating agent etc.) on structure, stability, surface acidity and textural properties. Here, catalyst -SO3H density and porosity (pore size, pore volume and surface area) had a direct effect on activity. Also, H2SO4 was less useful than 4-BDS (4-benzenediazoniumsulfoante) as a sulfonating agent. The best catalysts with mesoporous structure (average pore diameter 3.9-4.8 nm, pore volume 0.28-0.46 cm(3) g(-1)) and -SO3H density (0.70-0.84 mmol/g(cat)) were obtained by 4-BDS sulfonation of chemically activated DOWCs. In contrast, hydrothermal H2SO4 sulfonation of DOWC produced a non-porous catalyst with high -SO3H density while those obtained by H2SO4 treatment of activated biomass (AC) had a porous structure with low -SO3H density (0.19 mmol/gcat). Furthermore, the reported catalysts show excellent activity in two reactions of interest in biomass conversion: cellulose saccharification (glucose yield 35-53%) and fatty acid esterification (conversion upto 97%) outperforming H2SO4, conventional solid acids (zeolites, ion-exchange resins etc.) as well as sulfonated carbons reported earlier works, confirming their potential as alternative environmentally benign solid catalysts for sustainable, carbon efficient biorefining.

• 48. Korobov, Mikhail V.
Umeå University, Faculty of Science and Technology, Department of Physics.
Sorption of polar organic solvents and water by graphite oxide: thermodynamic approach2016In: Carbon, ISSN 0008-6223, E-ISSN 1873-3891, Vol. 102, 297-303 p.Article in journal (Refereed)

Sorption of polar organic solvents CH3OH, C4H8O (THF), CH3CN, C3H7NO (DMF), C2H6OS (DMSO), C5H9NO (NMP) and water was quantitatively evaluated for Hummers (H-GO) and Brodie (B-GO) graphite oxides at T = 298K and at melting temperature (Tm) of the solvents. H-GO showed stronger sorption compared to B-GO for all studied solvents and the increase of sorption upon lowering temperature was observed for both H-GO and B-GO. Thermodynamic equations allowed to explain earlier reported "maximums" of swelling/sorption in the binary systems H-GO – solvent at Tm. The specific relation between the values of enthalpies of sorption and melting leads to the change of sign in enthalpies of sorption at Tm and causes maximal swelling/sorption. The same thermodynamic explanation was given for the "maximum" on the swelling vs. pressure dependence in B-GO and H-GO – H2O systems earlier reported at pressure of phase transition "liquid water-ice VI". Notably higher sorption of H2O was observed for H-GO compared to H-GO membrane (H-GOm) at high relative humidity (RH), RH > 0.75. Experimental sorption isotherm of H-GOm was used to simulate permeation rates of water through H-GOm and to estimate effective diffusion coefficient of water through the membrane.

• 49.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Chemistry. Umeå University, Faculty of Science and Technology, Department of Plant Physiology. Umeå University, Faculty of Science and Technology, Umeå Plant Science Centre (UPSC). Umeå University, Faculty of Science and Technology, Department of Plant Physiology. Umeå University, Faculty of Science and Technology, Umeå Plant Science Centre (UPSC). Umeå University, Faculty of Science and Technology, Department of Chemistry.
Mobile hydrogen carbonate acts as proton acceptor in photosynthetic water oxidation2014In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 11, no 17, 6299-6304 p.Article in journal (Refereed)

Cyanobacteria, algae and plants oxidize water to the O2 we breathe, and consume CO2 during the synthesis of biomass. Although these vital processes are functionally and structurally well separated in photosynthetic organisms, there is a long-debated role for CO2/HCO3 in water oxidation. Using membrane-inlet mass spectrometry we demonstrate that HCO3 acts as a mobile proton acceptor that helps to transport the protons produced inside of photosystem II by water-oxidation out into the chloroplast's lumen, resulting in a light-driven production of O2 and CO2. Depletion of HCO3 from the media leads, in the absence of added buffers, to a reversible down-regulation of O2 production by about 20%. These findings add a previously unidentified component to the regulatory network of oxygenic photosynthesis, and conclude the more than 50-y-long quest for the function of CO2/ HCO3 in photosynthetic water oxidation.

• 50.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Charge Development at Iron Oxyhydroxide Surfaces: The Interplay between Surface Structure, Particle Morphology and Counterion Identity2014Doctoral thesis, comprehensive summary (Other academic)

Iron (oxyhydr)oxide (FeOOH) minerals play important roles in various natural, technological and societal settings. The widespread abundance of these minerals has prompted numerous studies on their surface reactivity in aqueous media. Surface charge development, one that namely takes place through the adsorption of potential determining ions (p.d.i.; H+, OH-) and coadsorption of counterions (e.g. Cl-, ClO4-, Na+), is particularly interesting in this regard. Mineral surface charge development is determined by numerous factors related to the interplay of mineral surface structure, particle morphology and counterion identity.

In this thesis the interplay between these factors is resolved by monitoring charge development on submicron-sized synthetic iron oxyhydroxide particles of different structures and sizes in aqueous media with counteranions of contrasting charge-to-size ratio (i.e. NaCl, NaClO4). This work, which is summarized in an introductory chapter and detailed in five appendices, is focused on three types of synthetic lepidocrocite (ã- FeOOH) of different shapes and surface roughness, three types of goethite (á-FeOOH) of different levels of surface roughness, and finally akaganéite (â-FeOOH), a mineral representing unique ion exchange properties due to its hollandite-type structure. While charge development was chiefly monitored by high precisition potentiometric titrations, these efforts were supported by a range of techniques including electrolyte ion uptake by cryogenic X-ray photoelectron spectroscopy, particle imaging by (high resolution) transmission electron microscopy, porosity analysis by N2 adsorption/desorption, surface potential development by electrokinetics, as well as thermodynamic adsorption modeling.

These efforts showed that lepidocrocite particles of contrasting morphology and surface roughness acquired highly comparable pH and ionic strength p.d.i. loadings. Equilibriation times required to develop these loadings were however altered when particles became aggregated by aging.

Goethite particles of contrasting surface roughness also acquired incongruent p.d.i. loadings, which were predominantly explained by the different charge-neutralizing capabilities of these surfaces, some of which were related to pore size distributions controlling the entrance of ions of contrasting sizes. Such size exclusion effects were also noted for the case of akaganéite where its bulk 0.4×0.4 nm wide channels permitted chloride diffusion but blocked perchlorate. Charge development at goethite surfaces in binary mixtures of NaCl and NaClO4 solutions also showed that the larger size-to-charge ratio chloride ion exerted a strong effect on these results even when present as a minor species. Many of these aforementioned effects were also modeled using variable, counterion- and loading-specific, Stern layer capacitance values.

The findings summarized in this thesis are providing a better understanding of surface processes occurring at iron oxyhydroxide surfaces. They should impact our ability in designing uses of such particles, for example, effective sorption in aquatic media, as well as to understand how they behave in natural systems.

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