Photon Energy (Czechia)

Operando, spatiotemporal resolved synchrotron X-ray fluorescence mapping measurements on a custom aqueous Zn/α-MnO2 cell provided direct, quantitative evidence of a Mn dissolution-deposition faradaic mechanism that governs the electrochemistry.

This work describes the preparation of a new thiosemicarbazone derivative, (Z)-N-ethyl-2-(6-oxo-1,10-phenanthrolin-5(6H)-ylidene)hydrazinecarbothioamide (phet) and its respective Re(i) tricarbonyl chloro complex, fac-[ReCl(CO)3(phet)]. The spectroscopic, photophysical and electrochemical properties of the new complex were fully investigated through steady state and time-resolved techniques along with computational calculations. In fac-[ReCl(CO)3(phet)], the new ligand is coordinated to the metal center through the pyridyl rings of the phenanthroline moiety. The unbound electron pairs in the S atom of the bending thiosemicarbazone group induce new low energy lying electronic transitions. Consequently, enhanced visible light absorption up to 550 nm is observed in acetonitrile due to the overlap between MLCTRe→phet and ILphet(n→π*) transitions. The absorption bands and emission quantum yields of fac-[ReCl(CO)3(phet)] are sensitive to proton concentration due to an acid-basic equilibrium in the N atoms of the thiosemicarbazone. Proton dissociation constants of 10.0 ± 0.1 and 11.4 ± 0.2 were determined respectively for the ground and excited states of the new complex. Spectral changes could also be observed in the presence of Zn2+ cations which can be further explored for sensing applications. The electrochemical behavior of the new complex was studied in detail, revealing up to four one electron reduction processes in the range from 0 to -2.4 V vs. Fc+/Fc. With support of DFT calculations, the first three processes are ascribed to the reduction of the coordinated phet ligand followed by the ReI/0 reduction and consequent Cl- release. The new complex was able to act as an electrocatalyst for CO2 reduction into CO (Eonset = -1.92 V vs. Fc+/Fc), with a turnover frequency of 2.81 s-1 and turnover number of 24 ± 1 in anhydrous acetonitrile, being the first Re(i) tricarbonyl complex with a thiosemicarbazone derivative described for this goal. The detailed characterization carried out here can drive the development of new Re(i)-thiosemicarbazone derivatives for different applications.

In this chapter the generalized Harvey–Shack (GHS) surface scatter theory is numerically compared to the classical Rayleigh–Rice (RR) theory, which is a small perturbation method (SPM), the Kirchhoff approximation (KA) method, and the rigorous method of moments (MoM) for 1D ideally conducting surfaces whose surface power spectral density (PSD) function is Gaussian or exhibits an inverse power law (fractal) behavior. In spite of its simple analytic form, our numerical comparisons show that the new GHS theory is valid (with reasonable accuracy) over a broader range of surface parameter space than either of the two classical surface scatter theories.

The structural phase transformations in the chalcopyrite semiconductor AgInTe2 have been studied up to 10 GPa on both pressure increase and decrease. The experiment were carried out using angle-dispersive X-ray diffraction with synchrotron radiation and an image plate. The diffraction patterns of AgInTe2 at ambient pressure reveal two coexisting phases: the first has the chalcopyrite structure while the second has a zinc blende like structure. On pressure increase both phases transformed at 3-4 GPa to a cationdisordered structure with spacegroup Cmcm, the atomic coordinates of which -v=0.75 for Ag or In and v=0.25 for Te -correspond to an NaCl-like structure. On pressure increase the Cmcm phase was stable up to at least 10.25 GPa. On pressure decrease, the chalcopyrite phase started to reappear at 0.55 GPa, and the Cmcm phase disappeared completely at ambient pressure. In addition to the experimental study, we have also performed density functional theory calculations. The calculated transition pressure from the chalcopyrite phase to the Cmcm phase is 4.08 GPa, and the calculated atomic positions in the Cmcm phase are in excellent agreement with those determined experimentally.

We evaluated radiofrequency (RF) heating of a humerus implant embedded in a gel phantom during magnetic resonance (MR) imaging for the specific absorption rate (SAR), angle between the implant and static magnetic field (B(0)), and position of the implant in the irradiation coil. We embedded a stainless steel humerus implant 2 cm deep in tissue-equivalent loop and mass phantoms, placed it parallel to the static magnetic field of a 1.5T MR scanner, and recorded the temperatures of the implant surface with RF-transparent fiberoptic sensors. We measured rises in temperature at the tips of the implant by varying the SAR from 0.2 to 4.0 W/kg and evaluated RF heating of the implant for its angle to B(0) and its displacement along B(0) from the center of the RF irradiation coil. RF heating was similar for the loop and mass phantoms because the eddy current flows through the periphery of both. As the SAR increased, the temperature at the implant tip increased, and there was a linear relationship between the SAR and temperature rise. The values were 6.4 degrees C at 2.0 W/kg and 12.7 degrees C at 4.0 W/kg. Rise in temperature decreased steeply as the angle between the implant and B(0) surpassed 45 degrees . In addition, as the implant was displaced from the center of the RF coil to both ends, the rise in temperature decreased. The rise in temperature in deep tissue was estimated to be higher than 1.0 degrees C for SAR above 0.4 W/kg. RF heating was greatest when the implant was set parallel to B(0). In MR imaging of patients with implants, there is a risk of RF heating when the loop of the eddy current is formed inside the body.

Laser Technik JournalVolume 3, Issue 2 p. 2-3 InhaltFree Access Inhalt: Laser Technik Journal 2/2006 First published: 12 February 2007 https://doi.org/10.1002/latj.200790089AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume3, Issue2März 2006Pages 2-3 RelatedInformation