| 1. |
- Artiglia, Luca, et al.
(författare)
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A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
- 2017
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 8
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Tidskriftsartikel (refereegranskat)abstract
- Oxidation of bromide in aqueous environments initiates the formation of molecular halogen compounds, which is important for the global tropospheric ozone budget. In the aqueous bulk, oxidation of bromide by ozone involves a [Br center dot OOO-] complex as intermediate. Here we report liquid jet X-ray photoelectron spectroscopy measurements that provide direct experimental evidence for the ozonide and establish its propensity for the solution-vapour interface. Theoretical calculations support these findings, showing that water stabilizes the ozonide and lowers the energy of the transition state at neutral pH. Kinetic experiments confirm the dominance of the heterogeneous oxidation route established by this precursor at low, atmospherically relevant ozone concentrations. Taken together, our results provide a strong case of different reaction kinetics and mechanisms of reactions occurring at the aqueous phase-vapour interface compared with the bulk aqueous phase.
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| 2. |
- Brown, Matthew, et al.
(författare)
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Effect of Surface Charge Density on the Affinity of Oxide Nanoparticles for the Vapor–Water Interface
- 2013
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 29:16, s. 5023-5029
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Tidskriftsartikel (refereegranskat)abstract
- Using in-situ X-ray photoelectron spectroscopy at the vapor–water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye–Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups (≡Si–O–) by counterions in the condensed ion layer. The increased negative surface charge density results in an electrostatic repulsion from the vapor–water interface that is seen to a lesser extent for larger particles that have a reduced charge density in the XPS measurements. We compare the results and interpretation of the in-situ XPS and corrected Debye–Hückel theory for surface complexation calculations with traditional surface tension measurements. Our results show that controlling the surface charge density of colloid particles can regulate their adsorption to the interface between two dielectrics.
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| 3. |
- Ekholm, Victor, 1989-
(författare)
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Ion pairing and Langmuir-like adsorption at aqueous surfaces studied by core-level spectroscopy
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Surface-bulk equilibria for solutes in aqueous solutions are studied using X-ray Photoelectron Spectroscopy (XPS) with high surface and chemical sensitivity. In the first part, the results show a reduction of the biochemically relevant guanidinium ions’ surface propensity with the addition of disodium sulphate due to ion pairing with the strongly hydrated sulphate ion, which could have implications for protein folding. Thereafter, the work considers amphiphilic organic compounds related to atmospheric science where the surface propensities, orientations at the surface and solute-solute and solute-solvent interactions are investigated. In the second part, two linear organic ions are investigated both as single solutes and in mixture. Both organic ions are surface enriched on their own and even more in the mixed solute solution. Due to hydrophobic expulsion of the alkyl chains, ion pairing between the organic ions and van der Waals interaction, the organic ions seem to assemble in clusters with their alkyl chains pointing out of the surface. The third part also covers linear organic compounds but one at a time probing the surface concentration as a function of bulk concentration. A Langmuir-like adsorption behavior was observed and Gibb’s free energy of surface adsorption (ΔGAds) values were extracted. An empiric model for deriving values for ΔGAds is proposed based upon the seemingly linear change in ΔGAds per carbon when comparing alcohols of different chain lengths. The fourth part investigates the acid/base fraction at the surface as function of bulk pH. The most important factor for this fraction seems to be how the surface propensity varies with the charge state of the acid or base instead of a possible difference in pH or pKa value at the surface. In the fifth part the oxygen K-edge of aqueous carbonate and bicarbonate is probed with the bulk-sensitive Resonant Inelastic X-ray Scattering (RIXS) technique.
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| 4. |
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| 5. |
- Kong, Xiangrui, et al.
(författare)
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A continuous flow diffusion chamber study of sea salt particles acting as cloud nuclei: deliquescence and ice nucleation
- 2018
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Ingår i: Tellus, Series B: Chemical and Physical Meteorology. - : Stockholm University Press. - 0280-6509 .- 1600-0889. ; 70:1, s. 1-18
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Tidskriftsartikel (refereegranskat)abstract
- © 2018 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group. Phase changes of sea salt particles alter their physical and chemical properties, which is significant for Earth’s chemistry and energy budget. In this study, continuous flow diffusion chamber is used to investigate deliquescence, homogeneous and heterogeneous ice nucleation between 242K and 215K, of four salts: pure NaCl, pure MgCl 2 , synthetic sea water salt, and salt distilled from sampled sea water. Anhydrous particles, aqueous droplets and ice particles were discriminated using a polarisation-sensitive optical particle counter coupled with a machine learning analysis technique. The measured onset deliquescence relative humidities agree with previous studies, where sea water salts deliquescence at lower humidities than pure NaCl. Deliquesced salt droplets homogenously freeze when the relative humidity reaches a sufficiently high value at temperatures below 233K. From 224K and below, deposition nucleation freezing on a fraction of NaCl particles was observed at humidities lower than the deliquescence relative humidity. At these low temperatures, otherwise unactivated salt particles deliquesced at the expected deliquescence point, followed by homogeneous freezing at temperatures as low as 215K. Thus, the observed sea salt particles exhibit a triad of temperature-dependent behaviours. First, they act as cloud condensation particles (CCNs) > 233K, second they can be homogeneous freezing nuclei (HFNs) < 233K and finally they act as ice nucleating particles (INPs) for heterogeneous nucleation < 224K.
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| 6. |
- Kong, Xiangrui, et al.
(författare)
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Reversibly Physisorbed and Chemisorbed Water on Carboxylic Salt Surfaces under Atmospheric Conditions
- 2020
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 124:9, s. 5263-5269
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Tidskriftsartikel (refereegranskat)abstract
- Copyright © 2020 American Chemical Society. The particle-gas interface in aerosol systems is of essential importance because it is here that many key atmospheric processes occur. In this study, we employ ambient pressure X-ray photoelectron spectroscopy (APXPS) to investigate the surface properties and processes of an atmospherically relevant carboxylic salt, sodium acetate, at subdeliquescence conditions. From the depth profiles of the elemental ratios of sodium, oxygen, and carbon, we find that after deliquescence-efflorescence cycles the salt surface is sodium-depleted. The mechanism of the observed depletion is proposed to be (i) the formation of neutral acetic acid in the solution due to the nature of the basic salt; (ii) the selective surface enhancement of neutral molecules under aqueous condition; and (iii) a hypothetical kinetic barrier to re-homogenization due to spatial separation and special local conditions on the surface, resulting in varied local surface composition. When the relative humidity gradually increases and approaches the deliquescence point, both reversible water uptake and reversible surface dissociation are confirmed by near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy at the oxygen K-edge and sodium K-edge, respectively. The solvation of sodium requires a higher relative humidity than needed for water adsorption, which suggests that water molecules are taken up by the surface, but the solvation of the salt surface begins only when sufficient water molecules are present, to facilitate the process. The sodium-depleted surface requires additional adsorbed water to affect and dissolve the sodium ions in deeper regions.
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| 7. |
- Mellqvist, U. H., et al.
(författare)
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Epidemiology and clinical outcomes of light-chain amyloidosis in Sweden: A nationwide population-based study
- 2023
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Ingår i: European Journal of Haematology. - 0902-4441. ; 111:5, s. 697-705
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Tidskriftsartikel (refereegranskat)abstract
- Objectives: This study evaluated data from six Swedish national registries to fill current evidence gaps on the epidemiology, clinical burden, and overall survival (OS) associated with light-chain (AL) amyloidosis.Methods: Patients newly diagnosed with AL amyloidosis were identified using six linked Swedish nationwide population-based registers. For each case, individuals from the general population were selected and matched with a maximum ratio of 1:5 based on age, sex, calendar year, and county.Results: 846 patients newly diagnosed with AL amyloidosis and 4227 demographically matched individuals were identified. From 2011 to 2019, annual AL amyloidosis incidence increased from 10.5 to 15.1 cases per million. At baseline, patients with AL amyloidosis had a significantly higher disease burden including higher rates of cardiac and renal failure relative to the comparison group. Among patients with AL amyloidosis, 21.5% had incident heart failure and 17.1% had incident renal failure after initial diagnosis. Median OS for patients with AL amyloidosis was 56 months versus not reached in the matched general population comparison group.Conclusion: The incidence of newly diagnosed AL amyloidosis in Sweden increased over time with AL amyloidosis being associated with a higher risk of cardiac/renal failure and all-cause mortality compared with the general population.
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