Synthesis of Alkaline Earth Diazenides MAEN2 (MAE = Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

The alkaline earth diazenides MAEN2 with MAE = Ca, Sr and Ba were synthesized by a novel synthetic approach, namely, a controlled decomposition of the corresponding azides in a multianvil press at highpressure/ high-temperature conditions. The crystal structure of hitherto unknown calcium diazenide (space group I4/mmm (no. 139), a = 3.5747(6) Å, c = 5.9844(9) Å, Z = 2, wRp = 0.078) was solved and refined on the basis of powder X-ray diffraction data as well as that of SrN2 and BaN2. Accordingly, CaN2 is isotypic with SrN2 (space group I4/mmm (no. 139), a = 3.8054(2) Å, c = 6.8961(4) Å, Z = 2, wRp = 0.057) and the corresponding alkaline earth acetylenides (MAEC2) crystallizing in a tetragonally distorted NaCl structure type. In accordance with literature data, BaN2 adopts a more distorted structure in space group C2/c (no. 15) with a = 7.1608(4) Å, b = 4.3776(3) Å, c = 7.2188(4) Å, β = 104.9679(33)°, Z = 4 and wRp = 0.049). The N−N bond lengths of 1.202(4) Å in CaN2 (SrN2 1.239(4) Å, BaN2 1.23(2) Å) correspond well with a double-bonded dinitrogen unit confirming a diazenide ion [N2]2−. Temperature-dependent in situ powder X-ray diffractometry of the three alkaline earth diazenides resulted in formation of the corresponding subnitrides MAE2N (MAE = Ca, Sr, Ba) at higher temperatures. FTIR spectroscopy revealed a band at about 1380 cm−1 assigned to the N−N stretching vibration of the diazenide unit. Electronic structure calculations support the metallic character of alkaline earth diazenides

Density functional theory calculations of the carbon ELNES of small diameter armchair and zigzag nanotubes: core-hole, curvature and momentum transfer orientation effects

We perform density functional theory calculations on a series of armchair and zigzag nanotubes of diameters less than 1nm using the all-electron Full-Potential(-Linearised)-Augmented-Plane-Wave (FPLAPW) method. Emphasis is laid on the effects of curvature, the electron beam orientation and the inclusion of the core-hole on the carbon electron energy loss K-edge. The electron energy loss near-edge spectra of all the studied tubes show strong curvature effects compared to that of flat graphene. The curvature induced $\pi-\sigma$ hybridisation is shown to have a more drastic effect on the electronic properties of zigzag tubes than on those of armchair tubes. We show that the core-hole effect must be accounted for in order to correctly reproduce electron energy loss measurements. We also find that, the energy loss near edge spectra of these carbon systems are dominantly dipole selected and that they can be expressed simply as a proportionality with the local momentum projected density of states, thus portraying the weak energy dependence of the transition matrix elements. Compared to graphite, the ELNES of carbon nanotubes show a reduced anisotropy.Comment: 25 pages, 15 figures, revtex4 submitted for publication to Phys. Rev.

Principles of meiotic chromosome assembly revealed in S. cerevisiae

During meiotic prophase, chromosomes organise into a series of chromatin loops emanating from a proteinaceous axis, but the mechanisms of assembly remain unclear. Here we use Saccharomyces cerevisiae to explore how this elaborate three-dimensional chromosome organisation is linked to genomic sequence. As cells enter meiosis, we observe that strong cohesin-dependent grid-like Hi-C interaction patterns emerge, reminiscent of mammalian interphase organisation, but with distinct regulation. Meiotic patterns agree with simulations of loop extrusion with growth limited by barriers, in which a heterogeneous population of expanding loops develop along the chromosome. Importantly, CTCF, the factor that imposes similar features in mammalian interphase, is absent in S. cerevisiae, suggesting alternative mechanisms of barrier formation. While grid-like interactions emerge independently of meiotic chromosome synapsis, synapsis itself generates additional compaction that matures differentially according to telomere proximity and chromosome size. Collectively, our results elucidate fundamental principles of chromosome assembly and demonstrate the essential role of cohesin within this evolutionarily conserved process

Nearly Monodispersion CoSm Alloy Nanoparticles Formed by an In-situ Rapid Cooling and Passivating Microfluidic Process

An in siturapid cooling and passivating microfluidic processhas been developed for the synthesis of nearly monodispersed cobalt samarium nanoparticles (NPs) with tunable crystal structures and surface properties. This process involves promoting the nucleation and growth of NPs at an elevated temperature and rapidly quenching the NP colloids in a solution containing a passivating reagent at a reduced temperature. We have shown that Cobalt samarium NPs having amorphous crystal structures and a thin passivating layer can be synthesized with uniform nonspherical shapes and size of about 4.8 nm. The amorphous CoSm NPs in our study have blocking temperature near 40 K and average coercivity of 225 Oe at 10 K. The NPs also exhibit high anisotropic magnetic properties with a wasp-waist hysteresis loop and a bias shift of coercivity due to the shape anisotropy and the exchange coupling between the core and the thin oxidized surface layer

A pH sensor based on electric properties of nanotubes on a glass substrate

We fabricated a pH-sensitive device on a glass substrate based on properties of carbon nanotubes. Nanotubes were immobilized specifically on chemically modified areas on a substrate followed by deposition of metallic source and drain electrodes on the area. Some nanotubes connected the source and drain electrodes. A top gate electrode was fabricated on an insulating layer of silane coupling agent on the nanotube. The device showed properties of ann-type field effect transistor when a potential was applied to the nanotube from the top gate electrode. Before fabrication of the insulating layer, the device showed that thep-type field effect transistor and the current through the source and drain electrodes depend on the buffer pH. The current increases with decreasing pH of the CNT solution. This device, which can detect pH, is applicable for use as a biosensor through modification of the CNT surface

Optical response of finite-length carbon nanotubes

Optical response of finite-length metallic carbon nanotubes is calculated including effects of induced edge charges in a self-consistent manner. The results show that the main resonance corresponding to excitation of the fundamental plasmon mode with wave vector $\pi/l$ with $l$ being the tube length is quite robust and unaffected. This arises because the strong electric field associated with edge charges is screened and decays rapidly inside the nanotube. For higher-frequency resonances, the field starts to be mixed and tends to shift resonances to higher frequencies.Comment: 10 pages, 9 figures, to be published in J. Phys. Soc. Jp

What's the effect of the implementation of general practitioner cooperatives on caseload? Prospective intervention study on primary and secondary care

<p>Abstract</p> <p>Background</p> <p>Out-of-hours care in the primary care setting is rapidly changing and evolving towards general practitioner 'cooperatives' (GPC). GPCs already exist in the Netherlands, the United Kingdom and Scandinavia, all countries with strong general practice, including gatekeepers' role. This intervention study reports the use and caseload of out-of-hours care before and after implementation of a GPC in a well subscribed region in a country with an open access health care system and no gatekeepers' role for general practice.</p> <p>Methods</p> <p>We used a prospective before/after interventional study design. The intervention was the implementation of a GPC.</p> <p>Results</p> <p>One year after the implementation of a GPC, the number of patient contacts in the intervention region significantly increased at the GPC (OR: 1.645; 95% CI: 1.439-1.880), while there were no significant changes in patient contacts at the Emergency Department (ED) or in other regions where a simultaneous registration was performed. Although home visits decreased in all general practitioner registrations, the difference was more pronounced in the intervention region (intervention region: OR: 0.515; 95% CI: 0.411-0.646, other regions: OR: 0.743; 95% CI: 0.608-0.908). At the ED we observed a decrease in the number of trauma cases (OR: 0.789; 95% CI: 0.648-0.960) and of patients who came to hospital by ambulance (OR: 0.687; 95% CI: 0.565-0.836).</p> <p>Conclusions</p> <p>One year after its implementation more people seek help at the GPC, while the number of contacts at the ED remains the same. The most prominent changes in caseload are found in the trauma cases. Establishing a GPC in an open health care system, might redirect some patients with particular medical problems to primary care. This could lead to a lowering of costs or a more cost-effective out of hours care, but further research should focus on effective usage to divert patient flows and on quality and outcome of care.</p

Enhancement of the Electron Spin Resonance of Single-Walled Carbon Nanotubes by Oxygen Removal

We have observed a nearly fourfold increase in the electron spin resonance (ESR) signal from an ensemble of single-walled carbon nanotubes (SWCNTs) due to oxygen desorption. By performing temperature-dependent ESR spectroscopy both before and after thermal annealing, we found that the ESR in SWCNTs can be reversibly altered via the molecular oxygen content in the samples. Independent of the presence of adsorbed oxygen, a Curie-law (spin susceptibility $\propto 1/T$) is seen from $\sim$4 K to 300 K, indicating that the probed spins are finite-level species. For both the pre-annealed and post-annealed sample conditions, the ESR linewidth decreased as the temperature was increased, a phenomenon we identify as motional narrowing. From the temperature dependence of the linewidth, we extracted an estimate of the intertube hopping frequency; for both sample conditions, we found this hopping frequency to be $\sim$100 GHz. Since the spin hopping frequency changes only slightly when oxygen is desorbed, we conclude that only the spin susceptibility, not spin transport, is affected by the presence of physisorbed molecular oxygen in SWCNT ensembles. Surprisingly, no linewidth change is observed when the amount of oxygen in the SWCNT sample is altered, contrary to other carbonaceous systems and certain 1D conducting polymers. We hypothesize that physisorbed molecular oxygen acts as an acceptor ($p$-type), compensating the donor-like ($n$-type) defects that are responsible for the ESR signal in bulk SWCNTs.Comment: 14 pages, 7 figure

Thermodynamic model of hardness: Particular case of boron-rich solids

A number of successful theoretical models of hardness have been developed recently. A thermodynamic model of hardness, which supposes the intrinsic character of correlation between hardness and thermodynamic properties of solids, allows one to predict hardness of known or even hypothetical solids from the data on Gibbs energy of atomization of the elements, which implicitly determine the energy density per chemical bonding. The only structural data needed is the coordination number of the atoms in a lattice. Using this approach, the hardness of known and hypothetical polymorphs of pure boron and a number of boron-rich solids has been calculated. The thermodynamic interpretation of the bonding energy allows one to predict the hardness as a function of thermodynamic parameters. In particular, the excellent agreement between experimental and calculated values has been observed not only for the room- temperature values of the Vickers hardness of stoichiometric compounds, but also for its temperature and concentration dependencies