- 标题
- 摘要
- 关键词
- 实验方案
- 产品
-
The Catalytic Cycle of Water Oxidation in Crystallized Photosystem II Complexes: Performance and Requirements for Formation of Intermediates
摘要： Crystals of Photosystem II (PSII) contain the most homogeneous copies of the water-oxidizing reaction center where O2 is evolved (WOC). However, few functional studies of PSII operation in crystals have been carried out, despite their widespread use in structural studies. Here we apply oximetric methods to determine the quantum efficiency and lifetimes of intermediates of the WOC cycle as a function of added electron acceptors (quinones and ferricyanide), both aerobically and anaerobically. PSII crystals exhibit the highest quantum yield of O2 production yet observed of any native or isolated PSII (61.6%, theoretically 59,000 μmol O2/mg Chl/h). WOC cycling can be sustained for thousands of turnovers using an irreversible electron acceptor (ferricyanide). Simulations of the catalytic cycle identify four distinct photochemical inefficiencies in both PSII crystals and dissolved PSII cores that are nearly the same. The exogenous acceptors equilibrate with the native plastoquinone acceptor at the QB (or QC) site(s), for which two distinct redox couples are observable that regulate flux through PSII. Flux through the catalytic cycle of water oxidation is shown to be kinetically restricted by the QAQB two-electron gate. The lifetimes of the S2 and S3 states are greatly extended (especially S2) by electron acceptors and depend on their redox reversibility. PSII performance can be pushed in vitro far beyond what it is capable of in vivo. With careful use of precautions and monitoring of populations, PSII microcrystals enable the exploration of WOC intermediates and the mechanism of catalysis.
关键词： oxygen-evolving complex,electron acceptors,(micro)crystals,S states,quantum yield,Photosystem II
更新于2025-09-23 15:22:29
-
Up-conversion luminescence of RE3+ -doped polymer composites KGd(WO4)2&PMMA
摘要： Poly(methyl methacrylate) (PMMA)-based luminescent materials are of prime interest for many new optoelectronic devices. This work presents the spectroscopic properties of PMMA-based composites containing KGd(WO4)2:Yb3+/Er3+/Tm3+, KGd(WO4)2:Yb3+/Tm3+ and KGd(WO4)2:Yb3+/Er3+ powders. These systems exhibit effective multicolor up-conversion luminescence in VIS and NIR spectral range under 980 nm excitation. The vibrational properties of the composites were investigated for the first time using the μ-Raman spectroscopy. The obtained results suggest that the KGd(WO4)2:Yb3+/Er3+/Tm3+&PMMA integrated system can be successfully used as a new phosphor for the up-conversion based optoelectronic devices.
关键词： Micro-crystals,Rare earth ions,PMMA,KGd(WO4)2,Composites,Up-conversion
更新于2025-09-04 15:30:14