| 1. |
- Kiraev, Salauat R., et al.
(författare)
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Improved emission of Yb(iii) ions in triazacyclononane-based macrocyclic ligands compared to cyclen-based ones
- 2022
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry. - 1477-9226 .- 1477-9234. ; 51:43, s. 16596-16604
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Tidskriftsartikel (refereegranskat)abstract
- Yb(III) complexes based on ligands with a 1,4,7-triazacyclononane (tacn) macrocyclic core were synthesised. The complexes carry a 4-methoxymethyl-substituted carbostyril chromophore that serves as a light-harvesting antenna. The ligands supply 5 nitrogen and 3 oxygen donors via 1 methylenecarboxamide and 2 picolinate donors, creating +1 charged complexes with an octadentate binding environment. The electronic properties of the picolinates are modulated by varying the substitution at the 4 position with OMe, H, Cl, or CF3. Cyclic voltammetry indicated that the tacn-based Yb(III) complexes were easier to reduce than the analogous cyclen complexes. The first reductive event is likely picolinate-centred, followed by the formation of further reduced species. Antenna excitation yielded Yb(III) luminescence in the near-infrared (NIR) region in all cases. The antenna photophysical properties were consistent with intraligand photoinduced electron transfer from the excited carbostyril to the picolinate groups. The relative quantum yields of Yb(III) luminescence were determined. The lowest value was obtained for the complex with the most efficient antenna-to-picolinate photoinduced electron transfer. Despite intraligand electron transfer quenching of the antenna, the tacn-based Yb complexes were more emissive than their cyclen analogues, highlighting the influence of the ligand structure on the luminescence properties of NIR emissive lanthanide(III) ions.
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| 2. |
- Mathieu, Emilie, et al.
(författare)
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Sensitization Pathways in NIR-Emitting Yb(III) Complexes Bearing 0, +1, +2, or +3 Charges
- 2022
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 144:46, s. 21056-21067
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Tidskriftsartikel (refereegranskat)abstract
- Yb(III) complexes of macrocyclic ligands based on1,4,7,10-tetraazacyclododecane were synthesized. The ligands carried a carbostyril chromophore for Yb(III) sensitization, and carboxylate or carbamide donors for metal binding, forming complexes of 0, +1, +2, or +3 overall charge. The coordination geometry was little affected by the replacement of carboxylates with amides, as shown by paramagnetic 1H NMR spectroscopy. The Yb(III)/Yb(II) reduction potentials were dependent on the nature of the metal binding site, and the more positively charged complexes were easier to reduce. Carbostyril excitation resulted in Yb(III) luminescence in every complex. The residual carbostyril fluorescence quantum yields were smaller in complexes containing more reducible Yb(III) centers decreasing from 5.9% for uncharged complexes to 3.1−4.4% in +3 charged species, suggesting photoinduced electron transfer (PeT) from the antenna to the Yb(III). The relative Yb(III) luminescence quantum yields were identical within the experimental error, except for the +3 charged complex with fully methylated coordinating amides, which was the most intense Yb(III) emitter of the series in water. Quenching of the Yb(III) excited state by NH vibrations proved to limit Yb(III) emission. No clear improvement of the Yb(III) sensitization efficiency was shown upon faster PeT. This result can be explained by the concomitant sensitization of Yb(III) by phonon-assisted energy transfer (PAEnT) from the antenna triplet excited state, which was completely quenched in all of the Yb complexes. Depopulation of the triplet by PeT quenching of the donor singlet excited state would be compensated by the sensitizing nature of the PeT pathway, thus resulting in a constant overall sensitization efficiency across the series.
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| 3. |
- Prior, Matthew J., et al.
(författare)
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Arabidopsis bZIP11 Is a Susceptibility Factor during Pseudomonas syringae Infection
- 2021
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Ingår i: Molecular Plant-Microbe Interactions. - : American Phytopathological Society. - 0894-0282 .- 1943-7706. ; 34:4, s. 439-447
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Tidskriftsartikel (refereegranskat)abstract
- The induction of plant nutrient secretion systems is critical for successful pathogen infection. Some bacterial pathogens (e.g., Xanthomonas spp.) use transcription activator-like (TAL) effectors to induce transcription of SWEET sucrose efflux transporters. Pseudomonas syringae pv. tomato strain DC3000 lacks TAL effectors yet is able to induce multiple SWEETs in Arabidopsis thaliana by unknown mechanisms. Because bacteria require other nutrients in addition to sugars for efficient reproduction, we hypothesized that Pseudomonas spp. may depend on host transcription factors involved in secretory programs to increase access to essential nutrients. Bioinformatic analyses identified the Arabidopsis basic-leucine zipper transcription factor bZIP11 as a potential regulator of nutrient transporters, including SWEETs and UmamiT amino acid transporters. Inducible downregulation of bZIP11 expression in Arabidopsis resulted in reduced growth of P. syringae pv. tomato strain DC3000, whereas inducible overexpression of bZIP11 resulted in increased bacterial growth, supporting the hypothesis that bZIP11-regulated transcription programs are essential for maximal pathogen titer in leaves. Our data are consistent with a model in which a pathogen alters host transcription factor expression upstream of secretory transcription networks to promote nutrient efflux from host cells.
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| 4. |
- Tomar, Monika, et al.
(författare)
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Photocatalytic Generation of Divalent Lanthanide Reducing Agents
- 2023
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 145:41, s. 22555-22562
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Tidskriftsartikel (refereegranskat)abstract
- Divalent lanthanide (Ln) compounds are excellent reducing agents with unique reactivity profiles. These reagents are typically used in superstoichiometric amounts, often in combina-tion with harmful additives. Reactions catalytic in Ln(II) reagents that retain the reactivity and selectivity of the stoichiometric transformations are currently lacking due to the absence of effective and selective methods to form reactive Ln(II) species from stable precursors. Here, active Ln(II) is generated from a Ln(III) precursor through reduction by a photoexcited coumarin or carbostyril chromophore, which, in turn, is regenerated by a sacrificial reductant. The reductant can be metallic (Zn) or organic (amines) and can be used in strictly stoichiometric amounts. A broad range of reactions, including C-halogen, C=C, C=X (X = O, N), P=O, and N=N reductions, as well as C-C, C-X (X = N, S, P), and N-N couplings were readily carried out in yields and selectivities comparable to or better than those afforded by the analogous stoichiometric transformations. The reaction outcomes could be altered by changing the ligand or the lanthanide or through the addition of environmentally benign additives (e.g., water). EPR spectroscopy supported the formation of both Ln(II) and oxidized chromophore intermediates. Taken together, these results establish photochemical Ln(II) generation as a powerful strategy for rendering Ln(II)-mediated reactions catalytic.
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