Publications

Abstract The Dunaliella salina photosynthetic apparatus organization and function was investigated in wild type (WT) and a mutant (zea1) lacking all β,β-epoxycarotenoids derived from zeaxanthin (Z). The zea1 mutant lacked antheraxanthin, violaxanthin, and neoxanthin from its thylakoid membranes but constitutively accumulated Z instead. It also lacked the so-called xanthophyll cycle, which, upon irradiance stress, reversibly converts violaxanthin to Z via a de-epoxidation reaction. Despite the pronounced difference observed in the composition of β,β-epoxycarotenoids between WT and zea1, no discernible difference could be observed between the two strains in terms of growth, photosynthesis, organization of the photosynthetic apparatus, photo-acclimation, sensitivity to photodamage, or recovery from photo-inhibition. WT and zea1 were probed for the above parameters over a broad range of growth irradiance and upon light shift experiments (low light to high light shift and vice versa). A constitutive accumulation of Z in the zea1 strain did not affect the acclimation of the photosynthetic apparatus to irradiance, as evidenced by indistinguishable irradiance-dependent adjustments in the chlorophyll antenna size and photosystem content of WT and zea1 strain. In addition, a constitutive accumulation of Z in the zea1 strain did not affect rates of photodamage or the recovery of the photosynthetic apparatus from photo-inhibition. However, Z in the WT accumulated in parallel with the accumulation of photodamaged PSII centers in the chloroplast thylakoids and decayed in tandem with a chloroplast recovery from photo-inhibition. These results suggest a role for Z in the protection of photodamaged and disassembled PSII reaction centers, apparently needed while PSII is in the process of degradation and replacement of the D1/32-kD reaction center protein.

Efforts to heterologously produce quantities of isoprene hydrocarbons (C₅H₈) renewably from CO₂ and H₂O through the photosynthesis of cyanobacteria face barriers, including low levels of recombinant enzyme accumulation compounded by their slow innate catalytic activity. The present work sought to alleviate the "expression level" barrier upon placing the isoprene synthase (IspS) enzyme in different fusion configurations with the cpcB protein, the highly expressed β-subunit of phycocyanin. Different cpcB*IspS fusion constructs were made, distinguished by the absence or presence of linker amino acids between the two proteins. Composition of linker amino acids was variable with lengths of 7, 10, 16, and 65 amino acids designed to test for optimal activity of the IspS through spatial positioning between the cpcB and IspS. Results showed that fusion constructs with the highly expressed cpcB gene, as the leader sequence, improved transgene expression in the range of 61 to 275-fold over what was measured with the unfused IspS control. However, the specific activity of the IspS enzyme was attenuated in all fusion transformants, possibly because of allosteric effects exerted by the leader cpcB fusion protein. This inhibition varied depending on the nature of the linker amino acids between the cpcB and IspS proteins. In terms of isoprene production, the results further showed a trade-off between specific activity and transgenic enzyme accumulation. For example, the cpcB*L7*IspS strain showed only about 10% the isoprene synthase specific-activity of the unfused cpcB-IspS control, but it accumulated 254-fold more IspS enzyme. The latter more than countered the slower specific activity and made the cpcB*L7*IspS transformant the best isoprene producing strain in this work. Isoprene to biomass yield ratios improved from 0.2 mg g^-1 in the unfused cpcB-IspS control to 5.4 mg g^-1 in the cpcB*L7*IspS strain, a 27-fold improvement.

Developing multicharge and spin stabilization strategies is fundamental to enhancing the lifetime of functional organic materials, particularly for long-term energy storage in multiredox organic redox flow batteries. Current approaches are limited to the incorporation of electronic substituents to increase or decrease the overall electron density or bulky substituents to sterically shield reactive sites. With the aim to further expand the molecular toolbox for charge and spin stabilization, we introduce regioisomerism as a scaffold-diversifying design element that considers the collective and cumulative electronic and steric contributions from all of the substituents based on their relative regioisomeric arrangements. Through a systematic study of regioisomers of near-planar aromatic cyclic triindoles and nonplanar nonaromatic cyclic tetraindoles, we demonstrate that this regioisomeric engineering strategy significantly enhances the H-cell cycling stability in the above two new classes of 2e^- catholytes, even when current strategies failed to stabilize the multicharged species. Density functional theory calculations reveal that the strategy operates by redistributing the charge and spin densities while highlighting the role of aromaticity in charge stabilization. The most stable 2e^- catholyte candidate was paired with a viologen derivative anolyte to achieve a proof-of-concept all-organic flow battery with 1.26-1.49 V, 98% capacity retention, and only 0.0117% fade/h and 0.00563% fade/cycle over 400 cycles (192 h), which is the highest capacity retention ever reported over 400 cycles in a multielectron all-organic flow battery setup. We anticipate regioisomeric engineering to be a promising strategy complementary to conventional electronic and steric approaches for multicharge and spin stabilization in other functional organic materials.

Optical spectropolarimetry of the normal thermonuclear supernova SN2019np from -14.5 to +14.5 days relative to B-band maximum detected an intrinsic continuum polarization, p(cont), of 0.21+-0.09% at the first epoch. Between days -11.5 to +05, p(cont) remained about 0 and by day +14.5 was again significant at 0.19+-0.10%. Not considering the first epoch, the dominant axis of SiII(6355A) was roughly constant, staying close to the continuum until both rotated in opposite directions on day +14.5. Detailed radiation-hydrodynamical simulations produce a very steep density slope in the outermost ejecta so that the low first-epoch p(const) of about 0.2% nevertheless suggests a separate structure with an axis ratio of about 2 in the outer carbon-rich 3...5E-3 Mo. Large-amplitude fluctuations in the polarization profiles and a flocculent appearance of the polar diagram for the CaII near-infrared triplet (NIR3) may be related by a common origin. The temporal evolution of the polarization spectra agrees with an off-center delayed detonation. The late-time increase in polarization and the possible change in position angle are also consistent with an aspherical 56Ni core. The p(cont) and the absorptions due to Si II(6355A) and the CaII NIR3 form in the same region of the extended photosphere, with an interplay between line occultation and thermalization producing p. Small-scale polarization features may be due to small-scale structures, but many could be related to atomic patterns of the quasi-continuum; the hardly have an equivalent in the total-flux spectrum. We compare SN2019np to other SNe and develop future objectives and strategies for SNIa spectropolarimetry.

The product selectivity during 1,3-butadiene hydrogenation on monodisperse, colloidally synthesized, Pt nanoparticles was studied under reaction conditions with kinetic measurements and in situ sum frequency generation (SFG) vibrational spectroscopy. SFG was performed with the capping ligands intact in order to maintain nanoparticle size by reduced sintering. Four products are formed at 75 C: 1-butene, cis-2-butene, trans-2-butene, and n-butane. Ensembles of Pt nanoparticles with average diameters of 0.9 and 1.8 nm exhibit a ∼30% and ∼20% increase in the full hydrogenation products, respectively, as compared to Pt nanoparticles with average diameters of 4.6 and 6.7 nm. Methyl and methylene vibrational stretches of reaction intermediates observed under working conditions using SFG were used to correlate the stable reaction intermediates with the product distribution. Kinetic and SFG results correlate with previous DFT predictions for two parallel reaction pathways of 1,3-butadiene hydrogenation. Hydrogenation of 1,3-butadiene can initiate with H-addition at internal or terminal carbons leading to the formation of 1-buten-4-yl radical (metallocycle) and 2-buten-1-yl radical intermediates, respectively. Small (0.9 and 1.8 nm) nanoparticles exhibited vibrational resonances originating from both intermediates, while the large (4.6 and 6.7 nm) particles exhibited vibrational resonances originating predominately from the 2-buten-1-yl radical. This suggests each reaction pathway competes for partial and full hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical Society.

We address the problem of balancing the traffic load in multi-hop wireless networks. We consider a point-to-point communicating network with a uniform distribution of source-sink pairs. When routing along shortest paths, the nodes that are centrally located forward a disproportionate amount of traffic. This translates into increased congestion and energy consumption. However, the maximum load can be decreased if the packets follow curved paths. We show that the optimum such routing scheme can be expressed in terms of geometric optics and computed by linear programming. We then propose a practical solution, which we call Curveball Routing which achieves results not much worse than the optimum.We evaluate our solution at three levels of fidelity: a Java high-level simulator, the ns2 simulator, and the Intel Mirage Sensor Network Testbed. Simulation results using the high-level simulator show that our solution successfully avoids the crowded center of the network, and reduces the maximum load by up to 40%. At the same time, the increase of the expected path length is minimal, i.e., only 8% on average. Simulation results using the ns2 simulator show that our solution can increase throughput on moderately loaded networks by up to 15%, while testbed results show a reduction in peak energy usage by up to 25%. Our prototype suggests that our solution is easily deployable.

Gotcha! Using electrochemical surface-enhanced Raman spectroscopy, surface-bound hydroxyperoxy (AuOOH) is pinpointed in situ as a reaction intermediate of oxygen evolution on gold catalyst (see picture). Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Proposes a new approach for vision-based longitudinal and lateral vehicle control. The novel feature of this approach is the use of binocular vision. We integrate two modules consisting of a new, domain-specific, efficient binocular stereo algorithm, and a lane marker detection algorithm, and show that the integration results in a improved performance for each of the modules. Longitudinal control is supported by detecting and measuring the distances to leading vehicles using binocular stereo. The knowledge of the camera geometry with respect to the locally planar road is used to map the images of the road plane in the two camera views into alignment. This allows us to separate image features into those lying in the road plane, e.g. lane markers, and those due to other objects which are dynamically integrated into an obstacle map. Therefore, in contrast with the previous work, we can cope with the difficulties arising from occlusion of lane markers by other vehicles. The detection and measurement of the lane markers provides us with the positional parameters and the road curvature which are needed for lateral vehicle control. Moreover, this information is also used to update the camera geometry with respect to the road, therefore allowing us to cope with the problem of vibrations and road inclination to obtain consistent results from binocular stereo.< <ETX xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">&gt;</ETX>

The BL Lac type object 1ES 2344+51.4 (redshift z = 0.044) was one of the first sources to be included in the extreme high-peaked BL Lac (EHBL) family. EHBLs are characterised by a broadband spectral energy distribution (SED) featuring the synchrotron peak above ∼ 1017 Hz. From previous studies of 1ES 2344+51.4 in the very-high-energy (VHE, >100 GeV) gamma-ray range, its inverse Compton (IC) peak is expected around 200 GeV. 1ES 2344+51.4 was first detected in the VHE range by Whipple in 1995 during a very bright outburst showing around 60% of the flux of the Crab Nebula above 350 GeV. In 1996, during another flare in the X-ray band, observations with Beppo-SAX revealed a large 0.1-10 keV flux variability on timescales of a few hours and an impressive frequency shift of the synchrotron peak to above 1018 Hz. Later on, this extreme behaviour of the source motivated several multiwavelength campaigns, during most of which the source appeared to be in a low state and showing no clear signs of “extremeness”. In August 2016, FACT detected 1ES 2344+51.4 in a high state and triggered multiwavelength observations. The VHE observations show a flux level similar to the historical maximum of 1995. The combination of MAGIC, FACT, and Fermi-LAT spectra provides an unprecedented characterisation of the IC peak. It is the first time that simultaneous HE and VHE data are presented for this object during a flaring episode. We find an atypically hard spectrum in the VHE γ-rays as well as a hard X-ray spectrum, revealing a renewed extreme behaviour.