Project description:Phytochromes are red-light photoreceptors that regulate light responses in plants, fungi, and bacteria via reversible photoconversion between red (Pr) and far-red (Pfr) light-absorbing states. Here we report the crystal structure at 2.9 A resolution of a bacteriophytochrome from Pseudomonas aeruginosa with an intact, fully photoactive photosensory core domain in its dark-adapted Pfr state. This structure reveals how unusual interdomain interactions, including a knot and an "arm" structure near the chromophore site, bring together the PAS (Per-ARNT-Sim), GAF (cGMP phosphodiesterase/adenyl cyclase/FhlA), and PHY (phytochrome) domains to achieve Pr/Pfr photoconversion. The PAS, GAF, and PHY domains have topologic elements in common and may have a single evolutionary origin. We identify key interactions that stabilize the chromophore in the Pfr state and provide structural and mutational evidence to support the essential role of the PHY domain in efficient Pr/Pfr photoconversion. We also identify a pair of conserved residues that may undergo concerted conformational changes during photoconversion. Modeling of the full-length bacteriophytochrome structure, including its output histidine kinase domain, suggests how local structural changes originating in the photosensory domain modulate interactions between long, cross-domain signaling helices at the dimer interface and are transmitted to the spatially distant effector domain, thereby regulating its histidine kinase activity.
Project description:Recently, the discovery of organometallic halide perovskites provides promising routes for fabricating optoelectronic devices with low cost and high performance. Previous experimental studies of MAPbI3 optoelectronic devices, such as photodetectors and solar cells, are normally based on polycrystalline films. In this work, a high-performance planar-type photodetector fabricated on the (100) facet of a MAPbI3 single crystal is proposed. We demonstrate that MAPbI3 photodetector based on single crystal can perform much better than that on polycrystalline-film counterpart. The low trap density of MAPbI3 single crystal accounts for the higher carrier mobility and longer carrier diffusion length, resulted in a significant performance increasement of MAPbI3 photodetector. Compared with similar planar-type photodetectors based on MAPbI3 polycrystalline film, our MAPbI3 single crystal photodetector showed excellent performance with good stability and durability, broader response spectrum to near-infrared region, about 10(2) times higher responsivity and EQE, and approximately 10(3) times faster response speed. These results may pave the way for exploiting high-performance perovskites photodetectors based on single crystal.
Project description:Nanocrystalline Ce-substituted yttrium iron garnet (YIG) powders of different compositions, Y3-x Ce x Fe5O12 (0 ≤ x ≤ 2.0), were synthesized by a combination of sol-gel auto-combustion and solid-state synthesis techniques. The as-obtained powder samples were sintered at 1150 °C for 10 h. The garnet structure formation is confirmed by the X-ray diffraction pattern, which shows that the calculated lattice parameter increased for x = 1.0 and shows a decreasing trend for x ≥ 1.0 with the addition of cerium ions. The lattice parameter increased from 12.38 Å to 12.41 Å for x ≤ 1.0 whereas it decreased from 12.412 Å to 12.405 Å with the cerium composition for x > 1.0. The average particle size determined by high resolution transmission electron microscopy is in the range of 50 to 90 nm and found to increase with the substitution of cerium ions in YIG. The room temperature magnetic parameters such as saturation magnetization, coercivity and remanence magnetization are greatly affected by the substitution of cerium ions. The values of saturation magnetization decrease from 25.5 to 15 emu g-1 whereas coercivity increases from 1 to 28 Oe with the substitution of cerium ions. The pure YIG sample shows polycrystalline nature that changed towards a single-crystal structure leading to a preferred-(100) orientation with the Ce substitution. The change from a ring to a spotty pattern observed in SAED confirmed the crystalline phase transformation and is well supported by HRTEM and magnetic measurements. The behavior of magnetic and electrical properties is well supported by the poly- and single-crystalline nature of YIG and Ce-YIG, respectively. The crystal structure transformation in YIG brought about by Ce substitution could unveil enormous opportunities in the preparation of single-crystal materials from their polycrystalline counterparts.
Project description:Single-molecule magnets (SMMs) are regarded as a class of promising materials for spintronic and ultrahigh-density storage devices. Tuning the magnetic dynamics of single-molecule magnets is a crucial challenge for chemists. Lanthanide ions are not only highly magnetically anisotropic but also highly sensitive to the changes in the coordination environments. We developed a feasible approach to understand parts of the magneto-structure correlations and propose to regulate the relaxation behaviors via rational design. A series of Co(II)-Dy(III)-Co(II) complexes were obtained using in situ synthesis; in this system of complexes, the relaxation dynamics can be greatly improved, accompanied with desolvation, via single-crystal to single-crystal transformation. The effective energy barrier can be increased from 293?cm(-1) (422?K) to 416?cm(-1) (600?K), and the tunneling relaxation time can be grown from 8.5?×?10(-4) s to 7.4?×?10(-2) s. These remarkable improvements are due to the change in the coordination environments of Dy(III) and Co(II). Ab initio calculations were performed to better understand the magnetic dynamics.
Project description:The redetermination of the title compound, sodium pertechnate, from single-crystal CCD data recorded both at 296 and 100 K confirms previous studies based on X-ray powder diffraction film data [Schwochau (1962 ▸). Z. Naturforsch. Teil A, 17, 630; Keller & Kanellakopulos (1963 ▸). Radiochim. Acta, 1, 107-108] and neutron powder diffraction data using the Rietveld method [Weaver et al. (2017 ▸). Inorg. Chem.12, 677-681], but reveals a considerable improvement in precision. The standard uncertainties of the room-temperature structure determination are about seven times lower than those of the neutron diffraction structure determination and about 13 times lower at 100 K, due to the decrease in the amplitude of librations. The crystal expansion could be approximated linearly with a thermal volumic expansion coefficient of 1.19 (12) × 10-4 K-1. NaTcO4 adopts the scheelite (CaWO4) structure type in space group type I41/a with Na and Tc atoms (both with site symmetry -4) replacing Ca and W atoms, respectively.
Project description:Clarifying critical differences in free charge generation and recombination processes between inorganic and organic semiconductors is important for developing efficient organic photoconversion devices such as solar cells (SCs) and photodetector. In this study, we analyzed the dependence of doping concentration on the photoconversion process at the organic pn-homojunction interface in a single organic semiconductor using the temperature dependence of J-V characteristics and energy structure measurements. Even though the organic pn-homojunction SC devices were fabricated using a single host material and the doping technique resembling an inorganic pn-homojunction, the charge generation and recombination mechanisms are similar to that of conventional donor/acceptor (D/A) type organic SCs; that is, the charge separation happens from localized exciton and charge transfer (CT) state being separated by the energy offset between adjacent molecules, and the recombination happens from localized charge carrier at two adjacent molecules. The determining factor for photoconversion processes is the localized nature of charges in organic semiconductors. The results demonstrated that controlling the delocalization of the charges is important to realize efficient organic photoconversion devices.
Project description:Realization of one-chip, ultra-large-area, coherent semiconductor lasers has been one of the ultimate goals of laser physics and photonics for decades. Surface-emitting lasers with two-dimensional photonic crystal resonators, referred to as photonic-crystal surface-emitting lasers (PCSELs), are expected to show promise for this purpose. However, neither the general conditions nor the concrete photonic crystal structures to realize 100-W-to-1-kW-class single-mode operation in PCSELs have yet to be clarified. Here, we analytically derive the general conditions for ultra-large-area (3~10 mm) single-mode operation in PCSELs. By considering not only the Hermitian but also the non-Hermitian optical couplings inside PCSELs, we mathematically derive the complex eigenfrequencies of the four photonic bands around the Γ point as well as the radiation constant difference between the fundamental and higher-order modes in a finite-size device. We then reveal concrete photonic crystal structures which allow the control of both Hermitian and non-Hermitian coupling coefficients to achieve 100-W-to-1-kW-class single-mode lasing.
Project description:Photocatalytic CO2 conversion promises an ideal route to store solar energy into chemical bonds. However, sluggish electron kinetics and unfavorable product selectivity remain unresolved challenges. Here, an ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate, and borate-anchored Co single atoms were separately loaded on ultrathin g-C3N4 nanosheets. The optimized nanocomposite photocatalyst produces CO and CH4 from CO2 and water under UV-vis light irradiation, exhibiting a 42-fold photoactivity enhancement compared with g-C3N4 and nearly 100% selectivity towards CO2 reduction. Experimental and theoretical results reveal that the ionic liquid extracts electrons and facilitates CO2 reduction, whereas Co single atoms trap holes and catalyze water oxidation. More importantly, the maximum electron transfer efficiency for CO2 photoreduction, as measured with in-situ μs-transient absorption spectroscopy, is found to be 35.3%, owing to the combined effect of the ionic liquid and Co single atoms. This work offers a feasible strategy for efficiently converting CO2 to valuable chemicals.