Sensory proteins must relay structural signals from the sensory site over large distances to regulatory output domains. Phytochromes are a major family of red-light sensing kinases that control diverse cellular functions in plants, bacteria, and fungi.1-9 Bacterial phytochromes consist of a photosensory core and a C-terminal regulatory domain.10,11 Structures of photosensory cores are reported in the resting state12-18 and conformational responses to light activation have been proposed in the vicinity of the chromophore.19-23 However, the structure of the signalling state and the mechanism of downstream signal relay through the photosensory core remain elusive. Here, we report crystal and solution structures of the resting and active states of the photosensory core of the bacteriophytochrome from Deinococcus radiodurans. The structures reveal an open and closed form of the dimeric protein for the signalling and resting state, respectively. This nanometre scale rearrangement is controlled by refolding of an evolutionarily conserved “tongue”, which is in contact with the chromophore. The findings reveal an unusual mechanism where atomic scale conformational changes around the chromophore are first amplified into an Ångström scale distance change in the tongue, and further grow into a nanometre scale conformational signal. The structural mechanism is a blueprint for understanding how the sensor proteins connect to the cellular signalling network.
All-inorganic colloidal perovskite quantum dots (QDs) based on cesium, lead, and halide have recently emerged as promising light emitting materials. CsPbBr QDs have also been demonstrated as stable two-photon-pumped lasing medium. However, the reported two photon absorption (TPA) cross sections for these QDs differ by an order of magnitude. Here we present an in-depth study of the TPA properties of CsPbBr QDs with mean size ranging from 4.6 to 11.4 nm. By using femtosecond transient absorption (TA) spectroscopy we found that TPA cross section is proportional to the linear one photon absorption. The TPA cross section follows a power law dependence on QDs size with exponent 3.3 ± 0.2. The empirically obtained power-law dependence suggests that the TPA process through a virtual state populates exciton band states. The revealed power-law dependence and the understanding of TPA process are important for developing high performance nonlinear optical devices based on CsPbBr nanocrystals.
Due to their superior photoluminescence (PL) quantum yield (QY) and tunable optical band gap, all-inorganic CsPbBr3 perovskite quantum dots (QDs) have attracted intensive attention for the application in solar cells, light emitting diodes (LED), photodetectors and laser devices. In this scenario, the stability of such materials becomes a critical factor to be revealed. We hereby investigated the long-term stability of as-synthesized CsPbBr3 QDs suspended in toluene at various environmental conditions. We found light illumination would induce drastic photo-degradation of CsPbBr3 QDs. The steady-state spectroscopy, transmission electron microscopy (TEM), and X-ray diffraction (XRD) verified that CsPbBr3 QDs tend to aggregate to form larger particles under continuous light soaking. In addition, decreasing PL QY of the QDs during light soaking indicates the formation of trap sites. Our work reveals that the main origin of instability in CsPbBr3 QDs and provides reference to engineer such QDs towards optimal device application.
Background: Near-infrared (NIR) fluorescent bacteriophytochromes are valuable for optical imaging in mammals. Results: Reversal of one position in the fluorescent phytochrome variant IFP1.4 led to the brightest monomeric NIR phytofluor known. Conclusion: Crystallography shows that limiting motion and changing polarity in the chromophore binding pocket increase fluorescence. Significance: Understanding the source of increased fluorescence in NIR fluorescent phytofluors is essential for further improving these novel imaging tools.
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