Dithiinmaleimide Functionalized ET Derivatives: Syntheses, Characterization and X-ray Structure

Dithiinmaleimide (ethylenedithio)tetrathiafulvalene (1) and N-phenyldithiinmaleimide (ethylenedithio)tetrathiafulvalene (2) have been synthesized from bis(tetraethylammonium)bis(ethylenedithiotetrathiafulvalenyldithiolato)-zincate (3) in high yields. Their electrochemical properties were investigated by cyclic voltammetry (CV) measurements which show two reversible redox potentials of the tetrathiafulvalene (TTF) moiety and an irreversible reduction potential of the maleimide ring. The X-ray structure of 1 shows close S···S contacts in the range of the van der Waals radii (3.6 Å) and hydrogen bonds between the maleimide unite

Left ventricular ejection time, not heart rate, is an independent correlate of aortic pulse wave velocity.

Salvi P, Palombo C, Salvi GM, Labat C, Parati G, Benetos A. Left ventricular ejection time, not heart rate, is an independent correlate of aortic pulse wave velocity. J Appl Physiol 115: 1610–1617, 2013. First published September 19, 2013; doi:10.1152/japplphysiol.00475.2013.— Several studies showed a positive association between heart rate and pulse wave velocity, a sensitive marker of arterial stiffness. However, no study involving a large population has specifically addressed the dependence of pulse wave velocity on different components of the cardiac cycle. The aim of this study was to explore in subjects of different age the link between pulse wave velocity with heart period (the reciprocal of heart rate) and the temporal components of the cardiac cycle such as left ventricular ejection time and diastolic time. Carotid-femoral pulse wave velocity was assessed in 3,020 untreated subjects (1,107 men). Heart period, left ventricular ejection time, diastolic time, and early-systolic dP/dt were determined by carotid pulse wave analysis with high-fidelity applanation tonometry. An inverse association was found between pulse wave velocity and left ventricular ejection time at all ages (25 years, r2 0.043; 25–44 years, r2 0.103; 45–64 years, r2 0.079; 65–84 years, r2 0.044; 85 years, r2 0.022; P 0.0001 for all). A significant (P 0.0001) negative but always weaker correlation between pulse wave velocity and heart period was also found, with the exception of the youngest subjects (P0.20). A significant positive correlation was also found between pulse wave velocity and dP/dt (P 0.0001). With multiple stepwise regression analysis, left ventricular ejection time and dP/dt remained the only determinant of pulse wave velocity at all ages, whereas the contribution of heart period no longer became significant. Our data demonstrate that pulse wave velocity is more closely related to left ventricular systolic function than to heart period. This may have methodological and pathophysiological implications

Structure and Magnetic Properties of the Radical Cation Salt of a TTF-based NiII Complex

Chemical oxidation of a TTF-based NiII complex with I2 produces the corresponding radical cation salt 1, [Ni2Cl2(L)2](I3)2(I5)2(I2)(H2O)2(C4H8O)3, (L=4,5-bis(2-pyridylmethylsulfanyl)-4',5'-ethylenedithiotetrathiafulvalene). The results of magnetic susceptibility measurements show the occurrence of intramolecular magnetic exchange interactions in 1. The lack of close S···S contacts, confirmed by crystal structure analysis, results in an insulating behavio

Bond energy/eond order relationships for N-O linkages and a quantitative measure of ionicity: the rôle of nitro groups in hydrogen bonding

The nitro group is active in metabolic systems and can be found as an integral part of a number of useful curative drugs and many toxic substances. The basis for much of this activity is not fully understood. It is not necessarily caused directly by through-bond electronic effects but may also be due to direct H-bonding to nitro or to indirect interference by the nitro group with existing H-bonding. An unusual effect of a nitro substituent on kinetic results from urethane addition/elimination reactions (Scheme 1) has been ascribed to some form of self-association, which was neither specified nor quantified. To investigate self-association phenomena caused by a nitro group, a bond energy/bond order formula for N–O bonds has been developed and then used to interpret relative amounts of covalent and ionic contributions to total N–O bond energy. Calculated bond energies were then used to obtain enthalpies of formation for H-bonds to nitro groups in crystals and in solution. Similar results from solution data reveal that direct H-bonding to nitro is much weaker than in crystals, unless intramolecular H-bonding can occur. The results revealed that the 'self-association' effects observed for nitro substituents in urethanes (Scheme 1) were not caused by nitro participating directly in intermolecular bonding to NH of another urethane but by an indirect intramolecular action of the nitro group on pre-existing normal NH–O amide/amide type H-bonding

In‐situ Bragg coherent X‐ray diffraction during tensile testing of an individual Au nanowire

Nanomechanical testing methods have drawn significant attention in both scientific and industrial research fields owing to unique deformation mechanisms in constrained volumes that underpin new property regimes. In-situ imaging equipment is now routinely employed to monitor the live evolution of material response during mechanical loading, with many of the testing developments tailored for electron microscopes (EMs). More recently, progress towards quantitative in-situ testing at synchrotron beamlines1–3 enabled by innovations in source brightness, focusing optics, and large size detectors has been made. Novel techniques such as Bragg coherent X-ray diffraction promise 3D information with phase information related to displacement fields (elastic strain, defects) within the material. However, despite the rich information that can be collected, many challenges arise in the realization of in-situ imaging of single nanostructures using such methods, including meticulous sample preparation and complex data analysis in retrieving phase information. In this work, we present the first successful systematic single nanowire tensile test while simultaneously recording 3D Bragg peaks using coherent X-rays. Defect free single crystalline \u3c110\u3e oriented Au nanowires were grown by physical vapor deposition4 and a 100 nm nanowire was harvested from the substrate and transferred to a nanotensile stage within a microelectromechanical system chip, which can be mounted to a coherent X-ray beamline. 3D Bragg peaks were recorded with nanofocused beam combined with 2D detector at each displacement step to discuss the evolution of strain and rotation of the nanowire during the tensile test. The movement of the peak sensitively depicted evolution of the deformation of the nanowire. In addition, the 3D Bragg coherent X-ray diffraction followed by phase retrieval has shown to reveal the internal strain state of nanostructure5 and this advanced technique is expected to reveal unique surface effects that mediate the overall mechanical performance of nano-scaled materials. 1. Cornelius, T. W. et al. In situ three-dimensional reciprocal-space mapping during mechanical deformation. J. Synchrotron Radiat. 19, 688–694 (2012). 2. Ren, Z. et al. Scanning force microscope for in situ nanofocused X-ray diffraction studies. J. Synchrotron Radiat. 21, 1128–1133 (2014). 3. Leclere, C. et al. In situ bending of an Au nanowire monitored by micro Laue diffraction. J. Appl. Crystallogr. 48, 291–296 (2015). 4. Richter, G. et al. Ultrahigh strength single crystalline nanowhiskers grown by physical vapor deposition. Nano Lett. 9, 3048–3052 (2009). 5. Haag, S. et al. Anomalous coherent diffraction of core-shell nano-objects: A methodology for determination of composition and strain fields. Phys. Rev. B 87, 35408 (2013)

Combined coherent x-ray micro-diffraction and local mechanical loading on copper nanocrystals

Coherent x-ray micro-diffraction and local mechanical loading can be combined to investigate the mechanical deformation in crystalline nanostructures. Here we present measurements of plastic deformation in a copper crystal of sub-micron size obtained by loading the sample with an Atomic Force Microscopy tip. The appearance of sharp features in the diffraction pattern, while conserving its global shape, is attributed to crystal defects induced by the tip

Stability and Electronic Properties of TiO2 Nanostructures With and Without B and N Doping

We address one of the main challenges to TiO2-photocatalysis, namely band gap narrowing, by combining nanostructural changes with doping. With this aim we compare TiO2's electronic properties for small 0D clusters, 1D nanorods and nanotubes, 2D layers, and 3D surface and bulk phases using different approximations within density functional theory and GW calculations. In particular, we propose very small (R < 0.5 nm) but surprisingly stable nanotubes with promising properties. The nanotubes are initially formed from TiO2 layers with the PtO2 structure, with the smallest (2,2) nanotube relaxing to a rutile nanorod structure. We find that quantum confinement effects - as expected - generally lead to a widening of the energy gap. However, substitutional doping with boron or nitrogen is found to give rise to (meta-)stable structures and the introduction of dopant and mid-gap states which effectively reduce the band gap. Boron is seen to always give rise to n-type doping while depending on the local bonding geometry, nitrogen may give rise to n-type or p-type doping. For under coordinated TiO2 surface structures found in clusters, nanorods, nanotubes, layers and surfaces nitrogen gives rise to acceptor states while for larger clusters and bulk structures donor states are introduced