Immobilization and electrochemical redox behavior of cytochrome c on fullerene film-modified electrodes

Two different fullerene film-modified electrodes were prepared and used for surface immobilization and electrochemical property investigation of horse heart cytochrome c (cyt c). Both a pristine fullerene film and fullerene-palladium (C(60)-Pd) polymer film-modified platinum, glassy carbon and indium-tin-oxide (ITO) electrodes were used. The immobilized cyt c was characterized by piezoelectric microgravimetry at a quartz crystal microbalance (QCM), UV-visible absorption, and X-ray photoelectron spectroscopy (XPS), as well as cyclic voltammetry (CV) techniques. The UV-visible spectral studies revealed a small blue shift of both the Soret and Q band of the heme moiety of cyt c, immobilized on the C(60)-Pd polymer film-modified ITO electrode, as compared to the bands of cyt c in solution suggesting that molecules of cyt c are densely packed onto the surface of the modified electrode. The CV studies revealed a quasi-reversible electrode behavior of the heme moiety indicating the occurrence of kinetically hindered electron transfer. A good agreement was found between the values of cyt c electrode surface coverage determined by piezoelectric microgravimetry and cyclic voltammetry. For piezoelectric microgravimetry, these values ranged from 0.5 x 10(-10) to 2.5 x 10(-10) mol cm(-2), depending upon the amount of cyt c present in solution and the time allowed for immobilization, which compared with a value of 3.6+/-0.4 x 10(-10) mol cm(-2) determined by CV. The possible mechanisms of cyt c immobilization on the C(60) film and C(60)-Pd film-modified electrodes are also discussed.     

f-Element/crown ether complexes: 21. Conformational changes in metal complexed versus hydrogen bonded benzo-15-crown-5 in the structure of [Y(OH2)3(NCMe)-(benzo-15-crown-5)][ClO4]3·benzo-15-crown-5·CH3CN

Crystalline [Y(OH₂)₃(NCMe)(benzo-15-crown-5)][ClO₄]₃·benzo-15-crown-5-CH₃CN can be obtained by slowly cooling a reaction mixture of Y(ClO₄)₃·n H₂O with benzo-15-crown-5 in a solution of acetonitrile and methanol (3 : 1) from 60°C to room temperature. The crystal structure of this complex has been determined at –150 and 20°C. The complex is triclinic,P . At –150°C the cell parameters area = 11.986(4),b = 12.071(7),c = 16.364(5) Å, = 93.56(3), = 98.68(3), = 109.68(4)°, vol = 2187 ų, andD _calc = 1.61 g cm^–3 forZ = 2 formula units. 3633 independently observed [F _o 5(F _o)] reflections were used in the final least-squares refinement leading to an agreement index ofR = 0.048. The Y(III) ion coordination geometry approximates a tricapped trigonal prism with three water molecules and three benzo-15-crown-5 oxygen atoms forming the prism, with the two remaining benzo-15-crown-5 oxygen atoms and the acetonitrile molecule completing the coordination as capping atoms. The three water molecules hydrogen bond a second crown ether molecule and two of the perchlorate anions. The two acetonitrile molecules have contacts with perchlorate oxygen atoms close enough for some weak interaction. One perchlorate is ordered, one is partially disordered as is the coordinated solvent molecule, and the third anion is totally disordered. The two unique crown ether molecules have distinctively different conformations.For Part 20, see reference [1].     

Iterative atmospheric correction scheme and the polarization color of alpine snow

Characterization of the Earth's surface is crucial to remote sensing, both to map geomorphological features and because subtracting this signal is essential during retrievals of the atmospheric constituents located between the surface and the sensor. Current operational algorithms model the surface total reflectance through a weighted linear combination of a few geometry-dependent kernels, each devised to describe a particular scattering mechanism. The information content of these measurements is overwhelmed by that of instruments with polarization capabilities: proposed models in this case are based on the Fresnel reflectance of an isotropic distribution of facets. Because of its remarkable lack of spectral contrast, the polarized reflectance of land surfaces in the shortwave infrared spectral region, where atmospheric scattering is minimal, can be used to model the surface also at shorter wavelengths, where aerosol retrievals are attempted based on well-established scattering theories.In radiative transfer simulations, straightforward separation of the surface and atmospheric contributions is not possible without approximations because of the coupling introduced by multiple reflections. Within a general inversion framework, the problem can be eliminated by linearizing the radiative transfer calculation, and making the Jacobian (i.e., the derivative expressing the sensitivity of the reflectance with respect to model parameters) available at output. We present a general methodology based on a Gauss–Newton iterative search, which automates this procedure and eliminates de facto the need of an ad hoc atmospheric correction.In this case study we analyze the color variations in the polarized reflectance measured by the NASA Goddard Institute of Space Studies Research Scanning Polarimeter during a survey of late-season snowfields in the High Sierra. This insofar unique dataset presents challenges linked to the rugged topography associated with the alpine environment and a likely high water content due to melting. The analysis benefits from ancillary information provided by the NASA Langley High Spectral Resolution Lidar deployed on the same aircraft.The results obtained from the iterative scheme are contrasted against the surface polarized reflectance obtained ignoring multiple reflections, via the simplistic subtraction of the atmospheric scattering contribution. Finally, the retrieved reflectance is modeled after the scattering properties of a dense collection of ice crystals at the surface. Confirming that the polarized reflectance of snow is spectrally flat would allow to extend the techniques already in use for polarimetric retrievals of aerosol properties over land to the large portion of snow-covered pixels plaguing orbital and suborbital observations.     

On Hybrid Ermakov-Painlevé Systems. Integrable Reduction

Hybrid Ermakov-Painlevé II-IV systems are introduced here in a unified manner. Their admitted Ermakov invariants together with associated canonical Painlevé equations are used to establish integrability properties.     

Sharp Morawetz estimates

We prove sharp Morawetz estimates — global in time with a singular weight in the spatial variables — for the linear wave, Klein-Gordon, and Schrödinger equations, for which we can characterise the maximisers. We also prove refined inequalities with respect to the angular integrability.     

Wave body interaction in 2D using smoothed particle hydrodynamics (SPH) with variable particle mass

Wave interaction with bodies is an important practical application for smoothed particle hydrodynamics (SPH) which in principle applies to steep and breaking waves without special treatment. However, few detailed tests have been undertaken even with small amplitude waves. In order to reduce computer time a variable particle mass distribution is tested here with fine resolution near the body and coarse resolution further away, while maintaining a uniform kernel size. We consider two well‐defined test cases, in two dimensions, of waves generated by a heaving semi‐immersed cylinder and progressive waves interacting with a fixed cylinder. But first, still water with hydrostatic pressure is tested. The open‐source code SPHysics ( http://www.sphysics.org )^{§Update made here after initial online publication.} is used with a Riemann solver in an Arbitrary Lagrangian–Eulerian formulation. For the heaving cylinder, SPH results for far field wave amplitude and cylinder force show good agreement with the data of Yu and Ursell (J. Fluid Mech. 1961; 11 :529–551). For wave loading on a half‐submerged cylinder the agreement with the experimental data of Dixon et al. (J. Waterway Port Coastal Ocean Div. 1979; 105 :421–438) for the root mean square force is within 2%. For more submerged cases, the results show some discrepancy, but this was also found with other modelling approaches. The sensitivity of results to the value of the slope limiter used in the MUSCL‐based Riemann solver is demonstrated. The variable mass distribution leads to a computer run speedup of nearly 200% in these cases. Copyright © 2011 John Wiley & Sons, Ltd.     

Transient spectroscopic characterization of the ring‐opening reaction of tetrahydrochromeno[2,3‐dimethyl]indole

Tetrahydrochromeno is a structural variant of spiropyran that undergoes a reversible ring‐opening to generate a colored nitrophenolate intermediate. Earlier work confirmed this intermediate through trimethylsilyl cyanide trapping under continuous irradiation. We have performed transient absorption spectroscopy to further characterize the mechanism of the ring‐opening reaction. Excitation at 355 nm produced a transient species with an absorption maximum at 445 nm, which we assign to the nitrophenolate unit of the ring‐opened product. The transient absorption decays after ~970 ns with small optical density changes corresponding to a 0.15 quantum yield. Exposure to oxygen did not exhibit a significant deleterious effect on the photoisomerization of the chromeno dye. Time‐dependent density functional theory corroborated spectroscopic assignments of the starting chromeno and the putative ring‐opened intermediate. The excited state behavior of this system parallels the structurally similar oxazine system reported by Raymo and coworkers. The one significant difference is the longer lifetime of the photochemically generated intermediate from chromeno. Copyright © 2015 John Wiley & Sons, Ltd.