ParaHydrogen Polarized Ethyl-[1-13C]pyruvate in Water,a Key Substrate for Fostering the PHIP-SAH Approach to Metabolic Imaging

An efficient synthesis of vinyl-[1-¹³C]pyruvate has been reported, from which ¹³C hyperpolarized (HP) ethyl-[1-¹³C]pyruvate has been obtained by means of ParaHydrogen Induced Polarization (PHIP). Due to the intrinsic lability of pyruvate, which leads quickly to degradation of the reaction mixture even under mild reaction conditions, the vinyl-ester has been synthesized through the intermediacy of a more stable ketal derivative. ¹³C and ¹H hyperpolarizations of ethyl-[1-¹³C]pyruvate, hydrogenated using ParaHydrogen, have been compared to those observed on the more widely used allyl-derivative. It has been demonstrated that the spin order transfer from ParaHydrogen protons to ¹³C, is more efficient on the ethyl than on the allyl-esterdue to the larger J-couplings involved. The main requirements needed for the biological application of this HP product have been met, i. e. an aqueous solution of the product at high concentration (40 mM) with a good ¹³C polarization level (4.8 %) has been obtained. The in vitro metabolic transformation of the HP ethyl-[1-¹³C]pyruvate, catalyzed by an esterase, has been observed. This substrate appears to be a good candidate for in vivo metabolic investigations using PHIP hyperpolarized probes.     

Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films

Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064     

AFM, SEM and GIXRD studies of thin films of red polycarbazolyldiacetylenes

In this paper we report the results of a morphological and structural investigation on film properties of a soluble polydiacetylene, the poly[1,6-bis(3,6-dihexadecyl-N-carbazolyl)-2,4-hexadiyne] (polyDCHD-HS). The red films of this polymer, prepared by standard spin-coating techniques, revealed absence of linear dichroism and birefringence in contrast with the ordered mesophases detected by powder X-ray studies. In order to interpret the optical behavior of this polymer, we performed AFM and SEM studies of polyDCHD-HS films spun on hydrophylic and hydrophobic glass substrates. We found the presence of surfaces organized in rod-like particles, more regularly oriented on the hydrophylic substrate. GIXRD studies, carried out on films sufficiently thick to allow the observation of the diffraction pattern, reveled the presence of a lamellar structure with a spacing of 3.22 nm. The low intensity of the diffraction peaks and the isotropic linear optical properties of the films show that the lamellar mesophases are not extended over large areas. These findings were compared with the data obtained from AFM and SEM studies on films of two other polydiacetylenes, the poly[1-(3,6-dihexadexyl-N-carbazolyl)-6-(N-carbazolyl)-2,4-hexadyine] (polya-DCHD) and the poly[1,6-bis(3,6-dipalmitoyl-N-carbazolyl)-2,4-hexadyine] (polyDPCHD), spun on hydrophylic glass substrate. The results confirmed the presence of nodular morphologies which seem to be a general characteristic of this class of materials. The particles organization appears instead related to the chemical nature of the substituents on the carbazolyl rings.     

Morphological and elemental characterisation with the high-energy ion-nanoprobe LIPSION

This contribution deals with the morphological and elemental characterisation with high-energy (MeV) focused ion beams (in particular protons) with special emphasis on high spatial resolution in the sub-micrometer regime and very low minimum detection limits (sub-ppm) in trace element analysis. The most important methods like particle induced X-ray emission (PIXE), Rutherford backscattering spectrometry (RBS), as well as scanning transmission ion microscopy (STIM) and STIM-tomography will be illustrated by examples from material and life sciences.     

The fluorite-related anion-excess structure of CeN0.222O0.667F1.333: Ordering of defect clusters

This investigation presents the preparation of CeN_0.222O_0.667F_1.333 by a solid-state reaction from a mixture of CeN:CeF₃:CeO₂ = 1:2:1.5 and its structural investigation. The samples were annealed at 900°C in platinum tubes for different times. The basic structure found by powder neutron diffraction is anion-excess fluorite-related. The unit cell is an orthorhombic distortion of the cubic fluorite cell and has the space group Abm2. The lattice constants are a = 577.71(2) pm, B = 572.76(5) pm, and c = 573.32(6) pm. The structure refined by Rietveld analysis shows that [1:0:2]- defect clusters are present. In samples prepared by longer annealing times an ordering of these clusters to larger aggregates, i.e., toward the vernier phases, was observed. This was deduced from full profile analysis without refining a structural model by comparing the instrumental resolution curves of several models.     

Spin-resolved photoemission from epitaxial Au layers on Pt(111): Coverage dependence of the bandstructure and evidence of surface resonances

Au/Pt(111) has been studied by spin-, angle- and energy-resolved photoemission with normal incident circularly polarized synchrotron radiation of BESSY and normal photoelectron emission for different Au coverages. The prepared layers were characterized by LEED and Augerelectron spectroscopy and turned out to grow up two dimensional and epitaxially. In the photoemission experiments the development of the 3-dimensional bandstructure in the -direction could be observed. For a coverage of 2.6 layers the highest occupied spin-orbit split bands are located at about 0.6 eV lower binding energy than the corresponding bands for a 3D-Au crystal and show dispersion which is, however, weaker than in a 3D-Au crystal. A 5 layer Au adsorbate was found to have already the same dispersion and energetic location as a Au(111)-crystal. For thick gold layers, which behave in photoemission like Au(111)-crystals, we find structures that cannot be due to direct transitions into a free electron like final band. The coverage dependence and spin polarization of these structures show that some of them are due to surface resonances, while the origin of one strong peak could not yet be explained conclusively. In addition we find strong hybridization and two avoided crossings in the occupied part of the bandstructure.