| 2. |
- Ngo, Son Tung, et al.
(författare)
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Distal Hydrophobic Loop Modulates the Copper Active Site and Reaction of AA13 Polysaccharide Monooxygenases
- 2022
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 126:39, s. 7567-7578
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Tidskriftsartikel (refereegranskat)abstract
- Polysaccharide monooxygenases (PMOs) use a type-2 copper center to activate O2 for the selective hydroxylation of one of the two C-H bonds of glycosidic linkages. Our electron paramagnetic resonance (EPR) analysis and molecular dynamics (MD) simulations suggest the unprecedented dynamic roles of the loop containing the residue G89 (G89 loop) on the active site structure and reaction cycle of starch-active PMOs (AA13 PMOs). In the Cu(II) state, the G89 loop could switch between an open and closed conformation, which is associated with the binding and dissociation of an aqueous ligand in the distal site, respectively. The conformation of the G89 loop influences the positioning of the copper center on the preferred substrate of AA13 PMOs. The dissociation of the distal ligand results in the bending of the T-shaped core of the Cu(II) active site, which could help facilitate its reduction to the active Cu(I) state. In the Cu(I) state, the G89 loop is in the closed conformation with a confined copper center, which could allow for efficient O2 binding. In addition, the G89 loop remains in the closed conformation in the Cu(II)-superoxo intermediate, which could prevent off-pathway superoxide release via exchange with the distal aqueous ligand. Finally, at the end of the reaction cycle, aqueous ligand binding to the distal site could switch the G89 loop to the open conformation and facilitate product release.
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| 3. |
- Chen, Qiaonan, 1992, et al.
(författare)
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Effects of Flexible Conjugation-Break Spacers of Non-Conjugated Polymer Acceptors on Photovoltaic and Mechanical Properties of All-Polymer Solar Cells
- 2022
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Ingår i: Nano-Micro Letters. - : Springer Science and Business Media LLC. - 2311-6706 .- 2150-5551. ; 14:1
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Tidskriftsartikel (refereegranskat)abstract
- Highlights: A series of non-conjugated acceptor polymers with flexible conjugation-break spacers (FCBSs) of different lengths were synthesized.The effect of FCBSs length on solubility of the acceptor polymers, and their photovoltaic and mechanical properties in all-polymer solar cells were explored.This work provides useful guidelines for the design of semiconducting polymers by introducing FCBS with proper length, which can giantly improved properties that are not possible to be achieved by the state-of-the-art fully conjugated polymers. Abstract: All-polymer solar cells (all-PSCs) possess attractive merits including superior thermal stability and mechanical flexibility for large-area roll-to-roll processing. Introducing flexible conjugation-break spacers (FCBSs) into backbones of polymer donor (PD) or polymer acceptor (PA) has been demonstrated as an efficient approach to enhance both the photovoltaic (PV) and mechanical properties of the all-PSCs. However, length dependency of FCBS on certain all-PSC related properties has not been systematically explored. In this regard, we report a series of new non-conjugated PAs by incorporating FCBS with various lengths (2, 4, and 8 carbon atoms in thioalkyl segments). Unlike common studies on so-called side-chain engineering, where longer side chains would lead to better solubility of those resulting polymers, in this work, we observe that the solubilities and the resulting photovoltaic/mechanical properties are optimized by a proper FCBS length (i.e., C2) in PA named PYTS-C2. Its all-PSC achieves a high efficiency of 11.37%, and excellent mechanical robustness with a crack onset strain of 12.39%, significantly superior to those of the other PAs. These results firstly demonstrate the effects of FCBS lengths on the PV performance and mechanical properties of the all-PSCs, providing an effective strategy to fine-tune the structures of PAs for highly efficient and mechanically robust PSCs.[Figure not available: see fulltext.]
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