Recombination dynamics in bacterial photosynthetic reaction centers

The time dependence of magnetic field effects on light absorption by triplet-state and radical ions in quinone-depleted reaction centers of Rhodopseudomonas sphaeroides strain R-26 has been investigated. Measurements on the time scale of the hyperfine interaction in the radical pair [(BChl)2+. ...BPh-.)] provided kinetic data characterizing the recombination process. The results have been interpreted in terms of a recently proposed model that assumes an intermediate electron acceptor (close site) between the bacteriochlorophyll "special pair" (BChl)2 and the bacteriopheophytin BPh (distant site). Recombination is assumed to proceed through this intermediate acceptor. The experiments led to effective recombination rates for the singlet and triplet channel: k(Seff) = 3.9 . 107 s-1 and k(Teff) = 7.4 . 10(8) s-1. These correspond to recombination rates ks = 1 . 10(1) s-1 and kT = 7.1 . 10(11) s-1 in the close configuration. The upper bound of the effective spin dephasing rate k2eff approximately equal to 1 . 10(9) s-1 is identical with the rate of the electron hopping between the distant site of zero spin exchange interaction and the close site of large interaction. Interpretation of data for the case of direct recombination yields the recombination rates, spin dephasing rate, and exchange interaction in a straightforward way

On the mechanism of photoinduced dimer dissociation in the plant UVR8 photoreceptor

UV-B absorption by the photoreceptor UV resistance locus 8 (UVR8) consisting of two identical protein units triggers a signal chain used by plants in connection with protection and repair of UV-B induced damage. X-ray structural analysis of the purified protein [Christie JM, et al. (2012) Science 335(6075):1492–1496] [Wu D, et al. (2012) Nature 484(7393): 214–220] has revealed that the dimer is held together by arginine–aspartate salt bridges. In this paper we address the initial processes in the signal chain. On the basis of high-level quantum-chemical calculations, we propose a mechanism for the photodissociation of UVR8 that consists of three steps: (i) In each monomer, multiple tryptophans form an extended light-harvesting system in which the L_a excited state of Trp233 experiences strong electrostatic stabilization by the protein environment. The strong stabilization singles out this tryptophan to be an efficient exciton acceptor that accumulates the excitation energy from the entire protein subunit. (ii) A fast decay of the locally excited state by charge separation generates the radical ion pair Trp285(+)-Trp233(−) with a dipole moment of ∼18 D. (iii) Key to the proposed mechanism is that this large dipole moment drives the breaking of the salt bridges between the two monomer subunits. The suggested mechanism for the UV-B–driven dissociation of the dimer that rests on the prominent players Trp233 and Trp285 explains the experimental results obtained from mutagenesis of UVR8

Simulation of space-borne tsunami detection using GNSS-Reflectometry applied to tsunamis in the Indian Ocean

Within the German-Indonesian Tsunami Early Warning System project GITEWS (Rudloff et al., 2009), a feasibility study on a future tsunami detection system from space has been carried out. The Global Navigation Satellite System Reflectometry (GNSS-R) is an innovative way of using reflected GNSS signals for remote sensing, e.g. sea surface altimetry. In contrast to conventional satellite radar altimetry, multiple height measurements within a wide field of view can be made simultaneously. With a dedicated Low Earth Orbit (LEO) constellation of satellites equipped with GNSS-R, densely spaced sea surface height measurements could be established to detect tsunamis. This simulation study compares the Walker and the meshed comb constellation with respect to their global reflection point distribution. The detection performance of various LEO constellation scenarios with GPS, GLONASS and Galileo as signal sources is investigated. The study concentrates on the detection performance for six historic tsunami events in the Indian Ocean generated by earthquakes of different magnitudes, as well as on different constellation types and orbit parameters. The GNSS-R carrier phase is compared with the PARIS or code altimetry approach. The study shows that Walker constellations have a much better reflection point distribution compared to the meshed comb constellation. Considering simulation assumptions and assuming technical feasibility it can be demonstrated that strong tsunamis with magnitudes (<i>M</i>) ≥8.5 can be detected with certainty from any orbit altitude within 15–25 min by a 48/8 or 81/9 Walker constellation if tsunami waves of 20 cm or higher can be detected by space-borne GNSS-R. The carrier phase approach outperforms the PARIS altimetry approach especially at low orbit altitudes and for a low number of LEO satellites

Determination of QA-content in bacterial reaction centers: an indispensable requirement for quantifying B-branch charge separation

AbstractWe have been able to determine the occupancy of the quinone site at the A-branch (QA) of a reaction center preparation with an accuracy of 2%. This is achieved by accumulating the P+Q−A state after multiple actinic excitation and monitoring the extent of the 30 ms ground state bleaching. This bleaching is corrected for deviations from complete saturation due to competing charge separation to the B-branch. On the other hand, knowledge of the QA content is indispensable for determining the yield of B-branch charge separation from nanosecond transients associated with the recombination of P+H−B, which have to be corrected for the nanosecond signal originating from P+H−A of RCs having lost QA

Time-resolved measurements of fluorescence from reaction centres of Rhodopseudomonas viridis and the effect of menaquinone reduction

AbstractThe kinetics of the fluorescence emitted by the ‘special pair’ of bacteriochlorophyll b molecules in reaction centres from Rhodopseudomonas viridis was recorded in the near infrared, with a time resolution of 1 ns. In nonreduced reaction centres two decay components were resolved with lifetimes of <0.5 and 2.5 ns. Upon reduction of the menaquinone electron acceptor three decay components were detected with lifetimes of < 0.5, 2.5 and 15ns

Modified reaction centers from Rhodobacter sphaeroides R26

Incubation of photosynthetic reaction centers from Rhodobacter sphaeroides R26 with exogenous 132-OH-bacteriochlorophyll ap or aGG according to Scheer et al. (1987) results in the exchange of endogenous bacteriochlorophyll ap. The exchange amounts to less-than-or-equals, slant 50% according to HPLC analysis, corresponding to a complete replacement of the ‘monomeric’ bacteriochlorophylls, bm and bl, by exogenous pigment. The absorption spectra show small, but distinct changes in the Qx-region of the bacteriochlorophylls, and bleaching of the modified reaction centers is retained. The corresponding binding sites must be accessible from the exterior, and allow for the introduction of a polar residue at C-132. This is supported by the observation of side reactions of the endogenous ‘monomeric’ bacteriochlorophylls within the reaction center pigments, e.g. epimerization and hydroxylation at C-132

Therapeutic and educational objectives in robot assisted play for children with autism

“This material is presented to ensure timely dissemination of scholarly and technical work. Copyright and all rights therein are retained by authors or by other copyright holders. All persons copying this information are expected to adhere to the terms and constraints invoked by each author's copyright. In most cases, these works may not be reposted without the explicit permission of the copyright holder." “Copyright IEEE. Personal use of this material is permitted. However, permission to reprint/republish this material for advertising or promotional purposes or for creating new collective works for resale or redistribution to servers or lists, or to reuse any copyrighted component of this work in other works must be obtained from the IEEE.” DOI: 10.1109/ROMAN.2009.5326251This article is a methodological paper that describes the therapeutic and educational objectives that were identified during the design process of a robot aimed at robot assisted play. The work described in this paper is part of the IROMEC project (Interactive Robotic Social Mediators as Companions) that recognizes the important role of play in child development and targets children who are prevented from or inhibited in playing. The project investigates the role of an interactive, autonomous robotic toy in therapy and education for children with special needs. This paper specifically addresses the therapeutic and educational objectives related to children with autism. In recent years, robots have already been used to teach basic social interaction skills to children with autism. The added value of the IROMEC robot is that play scenarios have been developed taking children's specific strengths and needs into consideration and covering a wide range of objectives in children's development areas (sensory, communicational and interaction, motor, cognitive and social and emotional). The paper describes children's developmental areas and illustrates how different experiences and interactions with the IROMEC robot are designed to target objectives in these areas.Final Published versio

Low-frequency optical phonon modes and carrier mobility in the halide perovskite CH_3NH_3PbBr_3 using terahertz time-domain spectroscopy

As a light absorber in photovoltaic applications, hybrid organic-inorganic halide perovskites should have long and balanced diffusion lengths for both the separated electrons and holes before recombination, which necessitates high carrier mobility. In polar semiconductors, the room-temperature carrier mobility is often limited by the scattering between carriers and the lowest-frequency optical phonon modes. Using terahertz time-domain spectroscopy, we examine the temperature evolution of these phonon modes in CH_3NH_3PbBr_3 and obtained high carrier mobility values using Feynman's polaron theory. This method allows us to estimate the upper limit of carrier mobilities without the need to create photogenerated free carriers, and can be applied to other heteropolar semiconductor systems with large polarons