1,665 research outputs found

    Structural transitions of monoolein bicontinuous cubic phase induced by inclusion of protein lysozyme solutions

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    Inclusion of protein lysozyme molecules in lipidic monoolein cubic phase induces a transition from a Pn3ˉm\rm Pn\bar{3}m structure to Im3ˉm\rm Im\bar{3}m one. Small-angle X-ray scattering (SAXS) method with high intensity synchrotron radiation enabled us to follow closely the transition depending on the conditions of lysozyme solutions. We showed that concentrated lysozyme solutions induced the appearance of the Im3ˉm\rm Im\bar{3}m structure coexisting with the Pn3ˉm\rm Pn\bar{3}m structure. From the relation between the lattice parameters of these two structures it was shown that they were related by the Bonnet transformation of underlying triply periodic minimal surfaces. We found that the transition also occurred at lower lysozyme concentration when NaCl induced attraction between lysozyme molecules. The origin of the transition was considered as a frustration in the cubic phase where lysozyme molecules were highly confined. A simple estimation of the frustration was given, which took into account of the translational entropy of lysozyme molecules. At the highest concentration of lysozyme and NaCl the Im3ˉm\rm Im\bar{3}m structure was found to disappear and left only the Pn3ˉm\rm Pn\bar{3}m structure. This was probably either due to the crystallization or phase separation of lysozyme solutions ongoing microscopically, which absorbed lysozyme molecules from channels of the cubic phase and thus removed the frustration.Comment: 8 pages, 5 figure

    Disc antenna enhanced infrared spectroscopy: From felf-assembled monolayers to membrane proteins

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    Plasmonic surfaces have emerged as a powerful platform for biomolecular sensing applications and can be designed to optimize the plasmonic resonance for probing molecular vibrations at utmost sensitivity. Here, we present a facile procedure to generate metallic microdisc antenna arrays that are employed in surface-enhanced infrared absorption (SEIRA) spectroscopy of biomolecules. Transmission electron microscopy (TEM) grids are used as shadow mask deployed during physical vapor deposition of gold. The resulting disc-shaped antennas exhibit enhancement factors of the vibrational bands of 4 × 104 giving rise to a detection limit <1 femtomol (10–15 mol) of molecules. Surface-bound monolayers of 4-mercaptobenzoic acid show polyelectrolyte behavior when titrated with cations in the aqueous medium. Conformational rigidity of the self-assembled monolayer is validated by density functional theory calculations. The membrane protein sensory rhodopsin II is tethered to the disc antenna arrays and is fully functional as inferred from the light-induced SEIRA difference spectra. As an advance to previous studies, the accessible frequency range is improved and extended into the fingerprint region

    CO2 efflux from leaf litter focused on spatial and temporal heterogeneity of moisture

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    Leaf litter respiration (R [LL]) was directly measured in situ to evaluate relationships with the water content in leaf litter (WC), which is distributed heterogeneously under natural conditions. To do so, we developed a small, closed static chamber system using an infrared gas analyzer, which can measure instantaneous R [LL]. This study focuses on the measurement of CO2 effluxes from leaf litter using the chamber system in the field and examines the relationship between R [LL] and WC among seven broadleaf species in a temperate forest. The measurements focused on the position of leaves within the litter layer, finding that both R [LL] and WC were significantly higher in the lower layer. The value of R [LL] increased with increasing WC, and the response of R [LL] to WC was similar among all seven species. Moreover, the temporal variation in WC differed among three species and was associated with leaf litter thickness. The observed heterogeneity in WC induced by the physical environment (e.g., position and thickness of leaf litter) affects the variation in WC and, therefore, both R [LL] and the decomposition rates of organic matter in the litter layer

    One year of continuous measurements of soil CH4 and CO2 fluxes in a Japanese cypress forest: Temporal and spatial variations associated with Asian monsoon rainfall

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    We examined the effects of Asian monsoon rainfall on CH[4] absorption of water-unsaturated forest soil. We conducted a 1 year continuous measurement of soil CH[4] and CO[2] fluxes with automated chamber systems in three plots with different soil characteristics and water content to investigate how temporal variations in CH[4] fluxes vary with the soil environment. CH[4] absorption was reduced by the “Baiu” summer rainfall event and peaked during the subsequent hot, dry period. Although CH[4] absorption and CO[2] emission typically increased as soil temperature increased, the temperature dependence of CH[4] varied more than that of CO[2], possibly due to the changing balance of activities between methanotrophs and methanogens occurring over a wide temperature range, which was strongly affected by soil water content. In short time intervals (30 min), the responses of CH[4] and CO[2] fluxes to rainfall were different for each plot. In a dry soil plot with a thick humus layer, both fluxes decreased abruptly at the peak of rainfall intensity. After rainfall, CO[2] emission increased quickly, while CH[4] absorption increased gradually. Release of accumulated CO[2] underground and restriction and recovery of CH[4] and CO[2] exchange between soil and air determined flux responses to rainfall. In a wet soil plot and a dry soil plot with a thinner humus layer, abrupt decreases in CH[4]fluxes were not observed. Consequently, the Asian monsoon rainfall strongly influenced temporal variations in CH[4] fluxes, and the differences in flux responses to environmental factors among plots caused large variability in annual budgets of CH[4] fluxes

    Aureochrome 1 illuminated: structural changes of a transcription factor probed by molecular spectroscopy.

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    Aureochrome 1 from Vaucheria frigida is a recently identified blue-light receptor that acts as a transcription factor. The protein comprises a photosensitive light-, oxygen- and voltage-sensitive (LOV) domain and a basic zipper (bZIP) domain that binds DNA rendering aureochrome 1 a prospective optogenetic tool. Here, we studied the photoreaction of full-length aureochrome 1 by molecular spectroscopy. The kinetics of the decay of the red-shifted triplet state and the blue-shifted signaling state were determined by time-resolved UV/Vis spectroscopy. It is shown that the presence of the bZIP domain further prolongs the lifetime of the LOV390 signaling state in comparison to the isolated LOV domain whereas bound DNA does not influence the photocycle kinetics. The light-dark Fourier transform infrared (FTIR) difference spectrum shows the characteristic features of the flavin mononucleotide chromophore except that the S-H stretching vibration of cysteine 254, which is involved in the formation of the thio-adduct state, is significantly shifted to lower frequencies compared to other LOV domains. The presence of the target DNA influences the light-induced FTIR difference spectrum of aureochrome 1. Vibrational bands that can be assigned to arginine and lysine side chains as well to the phosphate backbone, indicate crucial changes in interactions between transcription factor and DNA

    A Propossal to the Theory of Electrodynamics

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    Tables for Numerical Calculations of Complex Numbers

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    a Raman scattering study

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    The longitudinal optical phonon of metallic nanotubes shifts by 23 cm−1 to lower energies when the nanotubes are deposited from a solution onto a substrate. The linewidth increases by 13 cm−1. The changes are explained in terms of shifts in the Fermi energy that influence the Kohn anomaly in the longitudinal optical phonon branch in metallic nanotubes. Using in situ electrochemical Raman measurements we show that the Fermi energy is 0.16 eV below its intrinsic value in metallic nanotubes in solution. Our results impact the application of Raman spectroscopy to distinguish between metallic and semiconducting tubes by examining the high-energy mode line shape
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