Equilibrium of the reaction between dissolved sodium sulfide and biologically produced sulfur

The equilibrium of the heterogeneous reaction between dissolved sodium sulfide and biologically produced sulfur particles has been studied. Biologically produced sulfur was obtained from a bioreactor of a hydrogen sulfide removal process in which the dominating organism is Thiobacillus sp. W5. Detailed knowledge of this reaction is essential to understand its effect on the process. The results were compared with the equilibrium of the reaction of sulfide with ‘inorganic’ elemental sulfur. The equilibrium between dissolved sodium sulfide and biologically produced sulfur particles can be described by an equilibrium constant, K_x, which consists of a weighted sum of constants for polysulfide ions of different chain length, rather than a true single equilibrium constant. For biologically produced sulfur pK_x = 9.10 ± 0.08 (21 °C) and 9.17 ± 0.09 (35 °C) with an average polysulfide chain length x = 4.91 ± 0.32 (21 °C) and 4.59 ± 0.31 (35 °C). The pK_x value for biologically produced sulfur is significantly higher than for reaction of dissolved sodium sulfide with inorganic sulfur (pK_x = 8.82; 21 °C). This difference is probably caused by the negatively charged polymeric organic layer, which is present on biologically produced sulfur but absent with “inorganic” sulfur. Specific binding of polysulfide ions to the organic layer results in a higher polysulfide concentration at the reaction site compared to the bulk concentration. This results in an apparent decrease of the measured equilibrium constant, K_x.     

Time-resolved fluorescence analysis of the mobile flavin cofactor in p -hydroxybenzoate hydroxylase

Conformational heterogeneity of the FAD cofactor in p-hydroxybenzoate hydroxylase (PHBH) was investigated with time-resolved polarized flavin fluorescence. For binary enzyme/substrate (analogue) complexes of wild-type PHBH and Tyr222 mutants, crystallographic studies have revealed two distinct flavin conformations; the ‘in’ conformation with the isoalloxazine ring located in the active site, and the ‘out’ conformation with the isoalloxazine ring disposed towards the protein surface. Fluorescence-lifetime analysis of these complexes revealed similar lifetime distributions for the ‘in’ and ‘out’ conformations. The reason for this is twofold. First, the active site of PHBH contains various potential fluorescence-quenching sites close to the flavin. Fluorescence analysis of uncomplexed PHBH Y222V and Y222A showed that Tyr222 is responsible for picosecond fluorescence quenching free enzyme. In addition, other potential quenching sites, including a tryptophan and two tyrosines involved in substrate binding, are located nearby. Since the shortest distance between these quenching sites and the isoalloxazine ring differs only little on average, these aromatic residues are likely to contribute to fluorescence quenching. Second, the effect of flavin conformation on the fluorescence lifetime distribution is blurred by binding of the aromatic substrates: saturation with aromatic substrates induces highly efficient fluorescence quenching. The flavin conformation is therefore only reflected in the small relative contributions of the longer lifetimes.     

High-resolution non-invasive 3D imaging of paint microstructure by synchrotron-based X-ray laminography

The characterisation of the microstructure and micromechanical behaviour of paint is key to a range of problems related to the conservation or technical art history of paintings. Synchrotron-based X-ray laminography is demonstrated in this paper to image the local sub-surface microstructure in paintings in a non-invasive and non-destructive way. Based on absorption and phase contrast, the method can provide high-resolution 3D maps of the paint stratigraphy, including the substrate, and visualise small features, such as pigment particles, voids, cracks, wood cells, canvas fibres etc. Reconstructions may be indicative of local density or chemical composition due to increased attenuation of X-rays by elements of higher atomic number. The paint layers and their interfaces can be distinguished via variations in morphology or composition. Results of feasibility tests on a painting mockup (oak panel, chalk ground, vermilion and lead white paint) are shown, where lateral and depth resolution of up to a few micrometres is demonstrated. The method is well adapted to study the temporal evolution of the stratigraphy in test specimens and offers an alternative to destructive sampling of original works of art.     

Effects of Refractive Index and Viscosity on Fluorescence and Anisotropy Decays of Enhanced Cyan and Yellow Fluorescent Proteins

The fluorescence lifetime strongly depends on the immediate environment of the fluorophore. Time-resolved fluorescence measurements of the enhanced forms of ECFP and EYFP in water–glycerol mixtures were performed to quantify the effects of the refractive index and viscosity on the fluorescence lifetimes of these proteins. The experimental data show for ECFP and EYFP two fluorescence lifetime components: one short lifetime of about 1 ns and a longer lifetime of about 3.7 ns of ECFP and for EYFP 3.4. The fluorescence of ECFP is very heterogeneous, which can be explained by the presence of two populations: a conformation (67% present) where the fluorophore is less quenched than in the other conformation (33% present). The fluorescence decay of EYFP is much more homogeneous and the amplitude of the short fluorescence lifetime is about 5%. The fluorescence anisotropy decays show that the rotational correlation time of both proteins scales with increasing viscosity of the solvent similarly as shown earlier for GFP. The rotational correlation times are identical for ECFP and EYFP, which can be expected since both proteins have the same shape and size. The only difference observed is the slightly lower initial anisotropy for ECFP as compared to the one of EYFP.     

Enhancement of a 24.77-nm line emitted by the plasma of a boron nitride capillary discharge irradiated by a high-intensity ultrashort laser pulse

Investigations of plasma produced by a boron nitride capillary discharge irradiated with a guided 20-TW Ti: sapphire laser pulse at a peak intensity of 4 x 10(18) W/cm2 are presented. The guided laser radiation in the plasma channel generated He-like ions that, subject to suitable plasma temperature, recombined into Li-like nitrogen ions. Intense radiation at a wavelength of 24.77 nm was observed, indicating possible lasing at the 3d(5/2) - 2p(3/2) transition in Li-like nitrogen.     

Phase-matched nonlinear diffraction

We report on a new (to our knowledge) configuration incorporating both birefringence and quasi-phase-matching, enabling efficient phase-matched nonlinear diffraction in one-dimensional periodically poled nonlinear crystals. We demonstrate the method experimentally, showing an efficient nonlinear diffraction to the first few orders in two types of crystals, MgO doped congruent lithium niobate and congruent lithium niobate, and characterize its efficiency dependence on the fundamental power, the propagation angle, and the crystal temperature. This configuration can increase efficiencies observed in nonlinear diffraction experiments, enables ferroelectric domain characterization by nonlinear microscopy, and can be used to determine the duty cycles of periodically poled nonlinear crystals.     

Multiple Čerenkov second-harmonic waves in a two-dimensional nonlinear photonic structure

We report simultaneous generation of multiple conical second-harmonic waves in a two-dimensional nonlinear photonic structure when illuminated by two overlapping noncollinear fundamental beams. We show that this phenomenon is caused by the nonlinear ?erenkov radiation emitted due to the interaction of photons from each constituent fundamental beam as well as the virtual one propagating along the bisector of the two beams. In addition, by studying the asymmetric geometry of the interaction, we uniquely verify the effects of reciprocal vectors on the ?erenkov-type second-harmonic generation in nonlinear photonic structures.     

Polarization-mixing optical parametric oscillator

We report the experimental realization of a new type of optical parametric oscillator in which oscillation is achieved by polarization rotation in a linear retarder, followed by nonlinear polarization mixing. The mixing is performed by a type II degenerate parametric downconversion in a periodically poled KTP crystal pumped by a 1064 nm pulsed Nd:YAG pump. A single, linearly polarized beam, precisely at the degenerate wavelength is generated. The output spectrum has a narrow linewidth (below the instrumentation bandwidth of 1 nm) and is highly stable with respect to variations in the crystal temperature.     

A Scanning Electron Microscopy study of water in soil

Cold stage Scanning Electron Microscopy (SEM) with a rapid cooling technique makes it possible to investigate the water phase within unsaturated porous media. It is thought that this technique preserves the main features of the micromorphology of the water menisci as it exists in the liquid phase in soils. Saddle-shaped elements, as well as pendular rings of water, were observed with concave and convex curvatures of the water-air interface. The hydraulic conductivity of an unsaturated soil may be inferred from SEM photographs. Observations of isolated water menisci indicate the existence of an immobile water domain. The surface geometry of the water menisci was analyzed quantitatively and surface tension and capillary pressure were determined.     

On the transition moment of the CO2 40°1II-00°0 band near 7740 cm-1

Using intensity measurements on the CO₂ 40°1_II-00°0 band obtained by Valero and Boese, we have expanded the F(m)-factor for the parallel band by using the Herman-Wallis formula. We have calculated the transition moment and determined the coefficients in the expansion of F(m).