Photochemical Reductive trans-Elimination from trans-Diacidotetracyanoplatinate(IV) Complexes

Abstract Upon CT excitation the complex ions trans-[Pt(CN)4N3X]2- and trans-[Pt(CN)4X2]2- (X = Cl and Br) undergo a reductive trans-elimination with formation of [Pt(CN)4]2- and two ligand radicals in the photoprimary step. The formation of a Pt(III) intermediate is not observed. Due to the stability of [Pt(CN)4]2-, recombination reactions regenerating the starting complex are efficient if the ligand radicals are not scavenged. For the azide complexes the high quantum yields for the production of [Pt(CN)4]2- are explained by the instability of azide radicals. For trans-[Pt(CN)4X2]2-, the recombination is efficient in aqueous solution, while in ethanol the halogen atoms are scavenged by hydrogen abstraction. The sequence of steps following CT excitation can be explained by a potential energy diagram.</jats:p

Correlative Microscopy of Morphology and Luminescence of Cu porphyrin aggregates

Transfer of energy and information through molecule aggregates requires as one important building block anisotropic, cable-like structures. Knowledge on the spatial correlation of luminescence and morphology represents a prerequisite in the understanding of internal processes and will be important for architecting suitable landscapes. In this context we study the morphology, fluorescence and phosphorescence of molecule aggregate structures on surfaces in a spatially correlative way. We consider as two morphologies, lengthy strands and isotropic islands. It turns out that phosphorescence is quite strong compared to fluorescence and the spatial variation of the observed intensities is largely in line with the amount of dye. However in proportion, the strands exhibit more fluorescence than the isotropic islands suggesting weaker non-radiative channels. The ratio fluorescence to phosphorescence appears to be correlated with the degree of aggregation or internal order. The heights at which luminescence saturates is explained in the context of attenuation and emission multireflection, inside the dye. This is supported by correlative photoemission electron microscopy which is more sensitive to the surface region. The lengthy structures exhibit a pronounced polarization dependence of the luminescence with a relative dichroism up to about 60%, revealing substantial perpendicular orientation preference of the molecules with respect to the substrate and parallel with respect to the strands

Millimeter wave satellite concepts. Volume 1: Executive summary

The objectives of the program were: (1) development of methodology based on the technical requirements of potential services that might be assigned to millimeter wave bands for identifying the viable and appropriate technologies for future NASA millimeter research and development programs, and (2) testing of this methodology with user applications and services. The scope of the program included the entire communications network, both ground and space subsystems. The reports include: (1) cost, weight, and performance models for the subsystems, (2) conceptual design for point-to-point and broadcast communications satellites, (3) analytic relationships between subsystem parameters and an overall link performance, (4) baseline conceptual systems, (5) sensitivity studies, (6) model adjustment analyses, (7) identification of critical technologies and their risks, (8) brief R&D program scenarios for the technologies judged to be moderate or extensive risks

Calculation of coercivity of magnetic nanostructures at finite temperatures

We report a finite temperature micromagnetic method (FTM) that allows for the calculation of the coercive field of arbitrary shaped magnetic nanostructures at time scales of nanoseconds to years. Instead of directly solving the Landau-Lifshitz-Gilbert equation, the coercive field is obtained without any free parameter by solving a non linear equation, which arises from the transition state theory. The method is applicable to magnetic structures where coercivity is determined by one thermally activated reversal or nucleation process. The method shows excellent agreement with experimentally obtained coercive fields of magnetic nanostructures and provides a deeper understanding of the mechanism of coercivity.Comment: submitted to Phys. Rev.

Delivery of sTRAIL variants by MSCs in combination with cytotoxic drug treatment leads to p53-independent enhanced antitumor effects

Mesenchymal stem cells (MSCs) are able to infiltrate tumor tissues and thereby effectively deliver gene therapeutic payloads. Here, we engineered murine MSCs (mMSCs) to express a secreted form of the TNF-related apoptosis-inducing ligand (TRAIL), which is a potent inducer of apoptosis in tumor cells, and tested these MSCs, termed MSC.sTRAIL, in combination with conventional chemotherapeutic drug treatment in colon cancer models. When we pretreated human colorectal cancer HCT116 cells with low doses of 5-fluorouracil (5-FU) and added MSC.sTRAIL, we found significantly increased apoptosis as compared with single-agent treatment. Moreover, HCT116 xenografts, which were cotreated with 5-FU and systemically delivered MSC.sTRAIL, went into remission. Noteworthy, this effect was protein 53 (p53) independent and was mediated by TRAIL-receptor 2 (TRAIL-R2) upregulation, demonstrating the applicability of this approach in p53-defective tumors. Consequently, when we generated MSCs that secreted TRAIL-R2-specific variants of soluble TRAIL (sTRAIL), we found that such engineered MSCs, labeled MSC.sTRAIL DR5, had enhanced antitumor activity in combination with 5-FU when compared with MSC.sTRAIL. In contrast, TRAIL-resistant pancreatic carcinoma PancTu1 cells responded better to MSC.sTRAIL DR4 when the antiapoptotic protein XIAP (X-linked inhibitor of apoptosis protein) was silenced concomitantly. Taken together, our results demonstrate that TRAIL-receptor selective variants can potentially enhance the therapeutic efficacy of MSC-delivered TRAIL as part of individualized and tumor-specific combination treatments. © 2013 Macmillan Publishers Limited All rights reserved

The BeppoSAX view of the X-ray active nucleus of NGC4258

BeppoSAX observed NGC4258 on December 1998, when its 2-10 keV luminosity was \~1E41 erg/s. 100% variability is observed in the 3-10 keV band on timescales of a half a day while 20% variability is observed on timescales of one hour. The nuclear component is visible above 2 keV only, being obscured by a column density of (9.5+/-1.2)E22 cm-2; this component is detected up to 70 keV with S/N>=3 and with the steep power law energy index of 1.11+/-0.14. Bremsstrahlung emission for the 2-70 keV X-ray luminosity, as expected in ADAF models with strong winds, is ruled out by the data. The ratio between the nuclear radio and the X-ray luminosities is <=1E-5, similar to that of radio quiet AGN. X-ray variability and spectral shape, radio to X-ray and NIR to X-ray luminosity ratios suggest that the nucleus of NGC4258 could be a scaled-down version of a Seyfert nucleus. The soft (E<=2keV) X-ray emission is complex. There are at least two thermal-like components, with T1=0.6+/-0.1 keV and T2>=1.3 keV. The cooler (L(0.1-2.4keV)=1E40 erg/s) component is probably associated with the jet, resolved in X-rays by the ROSAT HRI. The second component, which can be modeled equally well by an unobscured power law model, has L(0.1-2.4keV)~7E39 erg/s, consistent with that expected from discrete X-ray sources in the host galaxy. NGC4258 and other maser AGNs show strong nuclear X-ray absorption. We propose that this large column of gas might be responsible for shielding the regions of maser emission from X-ray illumination. So a large column density gas may be a necessary property of masing AGNs.Comment: ApJ in pres

ROSAT Blank Field Sources I: Sample Selection and Archival Data

We have identified a population of blank field sources (or `blanks') among the ROSAT bright unidentified X-ray sources with faint optical counterparts. The extreme X-ray over optical flux ratio of blanks is not compatible with the main classes of X-ray emitters except for extreme BL Lacertae objects. From the analysis of ROSAT archival data we found no indication of variability and evidence for only three sources, out of 16, needing absorption in excess of the Galactic value. We also found evidence for an extended nature for only one of the 5 blanks with a serendipitous HRI detection; this source (1WGAJ1226.9+3332) was confirmed as a z=0.89 cluster of galaxies. Palomar images reveal the presence of a red (O-E~2) counterpart in the X-ray error circle for 6 blanks. The identification process brought to the discovery of another high z cluster of galaxies, one (possibly extreme) BL Lac, two ultraluminous X-ray sources in nearby galaxies and two apparently normal type1 AGNs. These AGNs, together with 4 more AGN-like objects seem to form a well defined group: they present unabsorbed X-ray spectra but red Palomar counterparts. We discuss the possible explanations for the discrepancy between the X-ray and optical data, among which: a suppressed big blue bump emission, an extreme dust to gas (~40-60 the Galactic ratio), a high redshift (z>3.5) QSO nature, an atypical dust grain size distribution and a dusty warm absorber. These AGN-like blanks seem to be the bright (and easier to study) analogs of the sources which are found in deep Chandra observations. Three more blanks have a still unknown nature.Comment: 23 pages, 8 figures, accepted by ApJ main journa

FACT -- The G-APD revolution in Cherenkov astronomy

Since two years, the FACT telescope is operating on the Canary Island of La Palma. Apart from its purpose to serve as a monitoring facility for the brightest TeV blazars, it was built as a major step to establish solid state photon counters as detectors in Cherenkov astronomy. The camera of the First G-APD Cherenkov Telesope comprises 1440 Geiger-mode avalanche photo diodes (G-APD), equipped with solid light guides to increase the effective light collection area of each sensor. Since no sense-line is available, a special challenge is to keep the applied voltage stable although the current drawn by the G-APD depends on the flux of night-sky background photons significantly varying with ambient light conditions. Methods have been developed to keep the temperature and voltage dependent response of the G-APDs stable during operation. As a cross-check, dark count spectra with high statistics have been taken under different environmental conditions. In this presentation, the project, the developed methods and the experience from two years of operation of the first G-APD based camera in Cherenkov astronomy under changing environmental conditions will be presented.Comment: Proceedings of the Nuclear Science Symposium and Medical Imaging Conference (IEEE-NSS/MIC), 201