| 1. |
- Berholts, Marta, et al.
(författare)
-
Photofragmentation of gas-phase acetic acid and acetamide clusters in the vacuum ultraviolet region
- 2017
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 147:19
-
Tidskriftsartikel (refereegranskat)abstract
- Photofragmentation of gas-phase acetamide and acetic acid clusters produced by a supersonic expansion source has been studied using time-of-flight mass spectrometry and the partial ion yield (PIY) technique combined with tunable vacuum-ultraviolet synchrotron radiation. Appearance energies of the clusters and their fragments were experimentally determined from the PIY measurements. The effect of clusterization conditions on the formation and fragmentation of acetic acid clusters was investigated. Ab initio quantum mechanical calculations were performed on both samples' dimers to find their neutral and ionized geometries as well as proton transfer energy barriers leading to the optimal geometries. In the case of the acetamide dimer, the reaction resulting in the production of ammoniated acetamide was probed, and the geometry of the obtained ion was calculated.
|
|
| 2. |
- Fukuzawa, Hironobu, et al.
(författare)
-
Real-time observation of X-ray-induced intramolecular and interatomic electronic decay in CH2I2
- 2019
-
Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 10:1
-
Tidskriftsartikel (refereegranskat)abstract
- The increasing availability of X-ray free-electron lasers (XFELs) has catalyzed the development of single-object structural determination and of structural dynamics tracking in real-time. Disentangling the molecular-level reactions triggered by the interaction with an XFEL pulse is a fundamental step towards developing such applications. Here we report real-time observations of XFEL-induced electronic decay via short-lived transient electronic states in the diiodomethane molecule, using a femtosecond near-infrared probe laser. We determine the lifetimes of the transient states populated during the XFEL-induced Auger cascades and find that multiply charged iodine ions are issued from short-lived (∼20 fs) transient states, whereas the singly charged ones originate from significantly longer-lived states (∼100 fs). We identify the mechanisms behind these different time scales: contrary to the short-lived transient states which relax by molecular Auger decay, the long-lived ones decay by an interatomic Coulombic decay between two iodine atoms, during the molecular fragmentation. © 2019, The Author(s).
|
|
| 3. |
- Itala, Eero, et al.
(författare)
-
Gas-phase study on uridine : Conformation and X-ray photofragmentation
- 2015
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 142:19
-
Tidskriftsartikel (refereegranskat)abstract
- Fragmentation of RNA nucleoside uridine, induced by carbon 1s core ionization, has been studied. The measurements by combined electron and ion spectroscopy have been performed in gas phase utilizing synchrotron radiation. As uridine is a combination of d-ribose and uracil, which have been studied earlier with the same method, this study also considers the effect of chemical environment and the relevant functional groups. Furthermore, since in core ionization the initial core hole is always highly localized, charge migration prior to fragmentation has been studied here. This study also demonstrates the destructive nature of core ionization as in most cases the C 1s ionization of uridine leads to concerted explosions producing only small fragments with masses <= 43 amu. In addition to fragmentation patterns, we found out that upon evaporation the sugar part of the uridine molecule attains hexagonal form.
|
|
| 4. |
- Itala, Eero, et al.
(författare)
-
Photofragmentation of Serine Following C 1s Core Ionization-Comparison with Cysteine
- 2016
-
Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 120:28, s. 5419-5426
-
Tidskriftsartikel (refereegranskat)abstract
- Photofragmentation pathways of doubly ionized serine molecules are investigated and compared with those of cysteine. The main motivation for the study is to investigate if an atomic substitution within the same group of elements, namely, replacing sulfur (in cysteine) with oxygen (in serine), causes a major change in the C 1s core ionization induced dissociation pattern in the molecules of an otherwise identical structure. The results show that in serine there is a single completely dominant fragmentation channel producing the (CNH2-4+, COH1-3+) pairs, whereas in cysteine there are also many other fragmentation channels. The employed experimental method was the photoelectron-photoion-photoion coincidence (PEPIPICO) technique combined with synchrotron radiation tuned to ionize desired core levels. Molecular dynamics calculations were also carried out in order to extract information on the fragmentation and the neutral final fragments.
|
|
| 5. |
- Kooser, Kuno, et al.
(författare)
-
Gas-phase endstation of electron, ion and coincidence spectroscopies for diluted samples at the FinEstBeAMS beamline of the MAX IV 1.5 GeV storage ring
- 2020
-
Ingår i: Journal of Synchrotron Radiation. - 0909-0495. ; 27, s. 1080-1091
-
Tidskriftsartikel (refereegranskat)abstract
- Since spring 2019 an experimental setup consisting of an electron spectrometer and an ion time-of-flight mass spectrometer for diluted samples has been available for users at the FinEstBeAMS beamline of the MAX IV Laboratory in Lund, Sweden. The setup enables users to study the interaction of atoms, molecules, (molecular) microclusters and nanoparticles with short-wavelength (vacuum ultraviolet and X-ray) synchrotron radiation and to follow the electron and nuclear dynamics induced by this interaction. Test measurements of N2 and thiophene (C4H4S) molecules have demonstrated that the setup can be used for many-particle coincidence spectroscopy. The measurements of the Ar 3p photoelectron spectra by linear horizontal and vertical polarization show that angle-resolved experiments can also be performed. The possibility to compare the electron spectroscopic results of diluted samples with solid targets in the case of Co2O3 and Fe2O3 at the Co and Fe L 2,3-absorption edges in the same experimental session is also demonstrated. Because the photon energy range of the FinEstBeAMS beamline extends from 4.4 eV up to 1000 eV, electron, ion and coincidence spectroscopy studies can be executed in a very broad photon energy range.
|
|
| 6. |
- Kooser, Kuno, et al.
(författare)
-
Operando high-temperature near-ambient pressure X-ray photoelectron spectroscopy and impedance spectroscopy study of Ni−Ce0.9Gd0.1O2−δ solid oxide fuel cell anode
- 2020
-
Ingår i: International Journal of Hydrogen Energy. - : Elsevier BV. - 0360-3199. ; 45:46, s. 25286-25298
-
Tidskriftsartikel (refereegranskat)abstract
- In this study we present the results of operando high temperature near-ambient-pressure x-ray photoelectron spectroscopy (HT-NAP-XPS) measurements of a pulsed laser deposited thin film Ni−Ce0.9Gd0.1O2−δ model electrode. In our measurements, we have used the novel three electrode dual-chamber electrochemical cell developed in our previous work at different H2 pressures and at different electrochemical conditions at around 650 °C. The possible redox reactions on the anode surface (Ni2+↔Ni0,Ce4+↔Ce3+) were investigated by HT-NAP-XPS technique simultaneously with electrochemical impedance spectroscopy measurements. The oxygen partial pressure in counter and reference electrode compartment was controlled at 0.2 bar. Changes in electronic structure of the Ce3d and Ni2p photoelectron spectra caused by electrode potential and H2 pressure variations were observed and estimated by curve fitting procedure. The O1s and valence band photoelectron signals were used for depth probing of the chemical composition and redox changes at Ni-GDC and for studying the influence of the electrochemical polarization on the chemical state of Ni-GDC surface atoms. As a result changes in oxidation state of electrode surface atoms caused by electrode polarization and oxide ion flux through the membrane were detected with simultaneous significant variation of electrochemical impedance.
|
|
| 7. |
- Levola, Helena, et al.
(författare)
-
Ionization-site effects on the photofragmentation of chloro- and bromoacetic acid molecules
- 2015
-
Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - : American Physical Society. - 1050-2947 .- 1094-1622. ; 92:6
-
Tidskriftsartikel (refereegranskat)abstract
- Fragmentation of gas-phase chloro-and bromoacetic acid samples, particularly its dependency on the atomic site of the initial core ionization, was studied in photoelectron-photoion-photoion coincidence (PEPIPICO) measurements. The fragmentation was investigated after ionizing carbon 1s and bromine 3d or chlorine 2p core orbitals. It was observed that the samples had many similar fragmentation pathways and that their relative weights depended strongly on the initial ionization site. Additional Auger PEPIPICO measurements revealed a clear dependence of fragment pair intensities on the kinetic energy of the emitted Auger electrons. The modeled and measured Auger electron spectra indicated that the average internal energy of the molecule was larger following the carbon 1s core-hole decay than after the decay of the halogen core hole. This difference in the internal energies was found to be the source of the site-dependent photofragmentation behavior.
|
|
| 8. |
- Nurk, Gunnar, et al.
(författare)
-
Near ambient pressure X-ray photoelectron - and impedance spectroscopy study of NiO - Ce 0.9 Gd 0.1 O 2-δ anode reduction using a novel dual-chamber spectroelectrochemical cell
- 2018
-
Ingår i: Journal of Power Sources. - : Elsevier BV. - 0378-7753. ; 378, s. 589-596
-
Tidskriftsartikel (refereegranskat)abstract
- This paper reports an experimental study, where the reduction of NiO-GDC to Ni-GDC is monitored using high temperature (HT) near ambient pressure (NAP) X-ray photoelectron spectroscopy (XPS) in combination with simultaneous impedance spectroscopy (IS). The experiment is carried out using a dual chamber (DC)-HT-NAP-XPS cell designed for membrane electrode studies. The dual chamber measurement cell enables adequate electrochemical feedback, i.e. the possibility of measuring the working electrode potential against a Pt reference electrode in a well-known environment (pO2 = 0.2 bar) and of monitoring the pO2 value on the studied electrode through open circuit voltage (OCV) measurements. Simultaneous changes of electrode impedance and O 1s, Ce 4d and Ni 3p electron binding energies are observed and discussed. The shape of the O 1s photoelectron peak is significantly influenced by the equilibria of Ce4+ ↔ Ce3+ and Ni2+ ↔ Ni0, influenced by pO2, in analysis chamber.
|
|
| 9. |
- Pihlava, Lassi, et al.
(författare)
-
Photodissociation of bromine-substituted nitroimidazole radiosensitizers
- 2023
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 25:18, s. 13004-13011
-
Tidskriftsartikel (refereegranskat)abstract
- Heavy elements and some nitroimidazoles both exhibit radiosensitizing properties through different mechanisms. In an effort to see how the overall radiosensitivity might be affected when the two radiosensitizers are combined in the same molecule, we studied the gas-phase photodissociation of two brominated nitroimidazoles and a bromine-free reference sample. Synchrotron radiation was employed to initiate the photodynamics and energy-resolved multiparticle coincidence spectroscopy was used to study the ensuing dissociation. We observed the brominated samples releasing high amounts of potentially radiosensitizing fragments upon dissociation. Since bromination also increases the likelihood of the drug molecule being ionised per a given X-ray dose, we conclude that heavy-element substitution of nitroimidazoles appears to be a viable path towards new, potent radiosensitizer drugs.
|
|
| 10. |
- Pihlava, Lassi, et al.
(författare)
-
Shell-dependent photofragmentation dynamics of a heavy-atom-containing bifunctional nitroimidazole radiosensitizer
- 2024
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 26:11, s. 8879-8890
-
Tidskriftsartikel (refereegranskat)abstract
- Radiation therapy uses ionizing radiation to break chemical bonds in cancer cells, thereby causing DNA damage and leading to cell death. The therapeutic effectiveness can be further increased by making the tumor cells more sensitive to radiation. Here, we investigate the role of the initial halogen atom core hole on the photofragmentation dynamics of 2-bromo-5-iodo-4-nitroimidazole, a potential bifunctional radiosensitizer. Bromine and iodine atoms were included in the molecule to increase the photoionization cross-section of the radiosensitizer at higher photon energies. The fragmentation dynamics of the molecule was studied experimentally in the gas phase using photoelectron-photoion-photoion coincidence spectroscopy and computationally using Born-Oppenheimer molecular dynamics. We observed significant changes between shallow core (I 4d, Br 3d) and deep core (I 3d) ionization in fragment formation and their kinetic energies. Despite the fact, that the ions ejected after deep core ionization have higher kinetic energies, we show that in a cellular environment, the ion spread is not much larger, keeping the damage well-localized. A study on photodissociation dynamics of 2-bromo-5-iodo-nitroimidazole - a model radiosensitizer - using coincidence spectroscopy and computational methods.
|
|
| 11. |
- Takahashi, Osamu, et al.
(författare)
-
Site-selective bond scission of methylbenzoate following core excitation
- 2018
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 20:14, s. 9591-9599
-
Tidskriftsartikel (refereegranskat)abstract
- The chemical bond scission of methylbenzoate (C6H5CO2CH3) following core excitation at the C and O K edges was examined from partial ion yield measurements across these edges using synchrotron radiation. Site-specific scission of the C-O bonds was observed at both edges. Theoretical X-ray absorption spectra (XAS) were obtained using density functional theory. Peak assignments in the observed spectra were found to be consistent with the theory. From core-excited state dynamics calculations, an elongation of the C-O bond was predicted and provides an explanation of the observed partial ion yield enhancement of CH3+ and C6H5CO+ at the core-excited resonances at both edges.
|
|
| 12. |
- Teppor, Patrick, et al.
(författare)
-
Unlocking the porosity of Fe-N-C catalysts using hydroxyapatite as a hard template en route to eco-friendly high-performance AEMFCs
- 2024
-
Ingår i: Journal of Power Sources. - : Elsevier BV. - 0378-7753 .- 1873-2755. ; 591
-
Tidskriftsartikel (refereegranskat)abstract
- In this work, we propose hydroxyapatite (HA) as a hard template to unlock the porosity of Fe-N-C catalyst materials. Using HA, a naturally occurring mineral that can be removed with nitric acid, in the synthesis generates a catalyst material with a unique porous network comprising abundant pores and interparticle cavities ranging from 10 to 3000 nm. Hard templating with HA alongside ZnCl2 as a micropore former results in a Fe-N-C catalyst based on naturally abundant peat with excellent oxygen reduction activity in alkaline conditions. A half -wave potential of 0.87 V vs RHE and a peak power density of 1.06 W cm-2 were achieved in rotating ring disk electrode and anion exchange membrane fuel cell experiments, respectively, rivaling the performance of other state-of-the-art platinum-free catalysts presented in the literature. A combined approach of using renewable peat as a carbon source and HA as a hard template offers an environmentally friendly approach to high-performance Fe-N-C catalysts with abundant porosity.
|
|
