| 1. |
- Slanina, Tomáš, et al.
(författare)
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Impact of Excited-State Antiaromaticity Relief in a Fundamental Benzene Photoreaction Leading to Substituted Bicyclo[3.1.0]hexenes
- 2020
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society. - 0002-7863 .- 1520-5126. ; 142:25, s. 10942-10954
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Tidskriftsartikel (refereegranskat)abstract
- Benzene exhibits a rich photochemistry which can provide access to complex molecular scaffolds that are difficult to access with reactions in the electronic ground state. While benzene is aromatic in its ground state, it is antiaromatic in its lowest ππ∗ excited states. Herein, we clarify to what extent relief of excited-state antiaromaticity (ESAA) triggers a fundamental benzene photoreaction: the photoinitiated nucleophilic addition of solvent to benzene in acidic media leading to substituted bicyclo[3.1.0]hex-2-enes. The reaction scope was probed experimentally, and it was found that silyl-substituted benzenes provide the most rapid access to bicyclo[3.1.0]hexene derivatives, formed as single isomers with three stereogenic centers in yields up to 75% in one step. Two major mechanism hypotheses, both involving ESAA relief, were explored through quantum chemical calculations and experiments. The first mechanism involves protonation of excited-state benzene and subsequent rearrangement to bicyclo[3.1.0]hexenium cation, trapped by a nucleophile, while the second involves photorearrangement of benzene to benzvalene followed by protonation and nucleophilic addition. Our studies reveal that the second mechanism is operative. We also clarify that similar ESAA relief leads to puckering of S1-state silabenzene and pyridinium ion, where the photorearrangement of the latter is of established synthetic utility. Finally, we identified causes for the limitations of the reaction, information that should be valuable in explorations of similar photoreactions. Taken together, we reveal how the ESAA in benzene and 6π-electron heterocycles trigger photochemical distortions that provide access to complex three-dimensional molecular scaffolds from simple reactants.
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| 2. |
- Alfredson, J., et al.
(författare)
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Design of a distributed human factors laboratory for future air systems
- 2018
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Ingår i: 31st Congress of the International Council of the Aeronautical Sciences, ICAS 2018. - : International Council of the Aeronautical Sciences. - 9783932182884
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Konferensbidrag (refereegranskat)abstract
- This paper presents a rationale for structuring a distributed human factors laboratory for future air systems. The distributed herein refers to two aspects: content and geographic. As for content, the laboratory is structured in two levels, namely, individual, and team. As for geographic, the laboratory infrastructure is distributed in three physically separate facilities, namely, Department of Computer and Information Science (IDA) and Department of Management and Engineering (IEI) from Linköping University - Sweden and the Competence Center in Manufacturing from the Aeronautics Institute of Technology (ITA) - Brazil.
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| 3. |
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| 4. |
- Papadakis, Raffaello, et al.
(författare)
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Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene
- 2016
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Ingår i: Nature Communications. - : Nature Publishing Group. - 2041-1723. ; 7
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Tidskriftsartikel (refereegranskat)abstract
- The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S 0), becomes exergonic in the first triplet state (T 1). This is in line with Baird's rule, which tells that benzene is antiaromatic and destabilized in its T 1 state and also in its first singlet excited state (S 1), opposite to S 0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T 1-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T 1 and S 1 states according to Baird's rule, is unreactive. Remarkably, also CVD-graphene on SiO 2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions. © The Author(s) 2016.
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| 5. |
- Quinto, Emiliano J., et al.
(författare)
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Predicting the concentration of verotoxin-producing Escherichia coli bacteria during processing and storage of fermented raw-meat sausages
- 2014
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Ingår i: Applied and Environmental Microbiology. - 0099-2240 .- 1098-5336. ; 80:9, s. 2715-2727
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Tidskriftsartikel (refereegranskat)abstract
- A model to predict the population density of verotoxigenic Escherichia coli (VTEC) throughout the elaboration and storage of fermented raw-meat sausages (FRMS) was developed. Probabilistic and kinetic measurement data sets collected from publicly available resources were completed with new measurements when required and used to quantify the dependence of VTEC growth and inactivation on the temperature, pH, water activity (aw), and concentration of lactic acid. Predictions were compared with observations in VTEC-contaminated FRMS manufactured in a pilot plant. Slight differences in the reduction of VTEC were predicted according to the fermentation temperature, 24 or 34°C, with greater inactivation at the highest temperature. The greatest reduction was observed during storage at high temperatures. A population decrease greater than 6 decimal logarithmic units was observed after 66 days of storage at 25°C, while a reduction of only ca. 1 logarithmic unit was detected at 12°C. The performance of our model and other modeling approaches was evaluated throughout the processing of dry and semidry FRMS. The greatest inactivation of VTEC was predicted in dry FRMS with long drying periods, while the smallest reduction was predicted in semidry FMRS with short drying periods. The model is implemented in a computing tool, E. coli SafeFerment (EcSF), freely available from http://www.ifr.ac.uk/safety/EcoliSafeFerment. EcSF integrates growth, probability of growth, and thermal and nonthermal inactivation models to predict the VTEC concentration throughout FRMS manufacturing and storage under constant or fluctuating environmental conditions. © 2014, American Society for Microbiology.
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