A Two-Coordinate Nickel Imido Complex That Effects C−H Amination

An exceptionally low coordinate nickel imido complex, (IPr*)Ni═N(dmp) (2) (dmp = 2,6-dimesitylphenyl), has been prepared by the elimination of N_2 from a bulky aryl azide in its reaction with (IPr*)Ni(η^6-C_7H_8) (1). The solid-state structure of 2 features two-coordinate nickel with a linear C−Ni−N core and a short Ni−N distance, both indicative of multiple-bond character. Computational studies using density functional theory showed a Ni═N bond dominated by Ni(dπ)−N(pπ) interactions, resulting in two nearly degenerate singly occupied molecular orbitals (SOMOs) that are Ni−N π* in character. Reaction of 2 with CO resulted in nitrene-group transfer to form (dmp)NCO and (IPr*)Ni(CO)_3 (3). Net C−H insertion was observed in the reaction of 2 with ethene, forming the vinylamine (dmp)NH(CH═CH_2) (5) via an azanickelacyclobutane intermediate, (IPr*)Ni{N,C:κ^2-N(dmp)CH_2CH_2} (4)

ELSID-diabetes study-evaluation of a large scale implementation of disease management programmes for patients with type 2 diabetes. Rationale, design and conduct : a study protocol

Background: Diabetes model projects in different regions of Germany including interventions such as quality circles, patient education and documentation of medical findings have shown improvements of HbA1c levels, blood pressure and occurrence of hypoglycaemia in before-after studies (without control group). In 2002 the German Ministry of Health defined legal regulations for the introduction of nationwide disease management programs (DMP) to improve the quality of care in chronically ill patients. In April 2003 the first DMP for patients with type 2 diabetes was accredited. The evaluation of the DMP is essential and has been made obligatory in Germany by the Fifth Book of Social Code. The aim of the study is to assess the effectiveness of DMP by example of type 2 diabetes in the primary care setting of two German federal states (Rheinland-Pfalz and Sachsen-Anhalt). Methods/Design: The study is three-armed: a prospective cluster-randomized comparison of two interventions (DMP 1 and DMP 2) against routine care without DMP as control group. In the DMP group 1 the patients are treated according to the current situation within the German-Diabetes-DMP. The DMP group 2 represents diabetic care within ideally implemented DMP providing additional interventions (e.g. quality circles, outreach visits). According to a sample size calculation a sample size of 200 GPs (each GP including 20 patients) will be required for the comparison of DMP 1 and DMP 2 considering possible drop-outs. For the comparison with routine care 4000 patients identified by diabetic tracer medication and age (> 50 years) will be analyzed. Discussion: This study will evaluate the effectiveness of the German Diabetes-DMP compared to a Diabetes-DMP providing additional interventions and routine care in the primary care setting of two different German federal states

Chaotic enhancement of dark matter density in binary systems

We study the capture of galactic dark matter particles (DMP) in two-body and few-body systems with a symplectic map description. This approach allows modeling the scattering of $10^{16}$ DMPs after following the time evolution of the captured particle on about $10^9$ orbital periods of the binary system. We obtain the DMP density distribution inside such systems and determine the enhancement factor of their density in a center vicinity compared to its galactic value as a function of the mass ratio of the bodies and the ratio of the body velocity to the velocity of the galactic DMP wind. We find that the enhancement factor can be on the order of tens of thousands.Comment: 6 pages, 9 figure

Wellcome DMP assessment rubric v2.0

This rubric is intended to assist in the assessment of Wellcome Trust data management plans, against the criteria required by the funder. It is not intended to be used as a template for researchers to follow when writing a data management plan. The rubric has been divided into 'performance criteria' (on the left hand side) which cover the information the funder expects to be included in the data management plan. Each performance criteria is followed by three descriptions of how it might be addressed, each indicating a different level of response. The descriptions are intended as examples of how the performance criteria might be addressed and are not considered to be exhaustive. The rubric also lists the documents and resources on which it was based

An anisotropic mesh adaptation method for the finite element solution of heterogeneous anisotropic diffusion problems

Heterogeneous anisotropic diffusion problems arise in the various areas of science and engineering including plasma physics, petroleum engineering, and image processing. Standard numerical methods can produce spurious oscillations when they are used to solve those problems. A common approach to avoid this difficulty is to design a proper numerical scheme and/or a proper mesh so that the numerical solution validates the discrete counterpart (DMP) of the maximum principle satisfied by the continuous solution. A well known mesh condition for the DMP satisfaction by the linear finite element solution of isotropic diffusion problems is the non-obtuse angle condition that requires the dihedral angles of mesh elements to be non-obtuse. In this paper, a generalization of the condition, the so-called anisotropic non-obtuse angle condition, is developed for the finite element solution of heterogeneous anisotropic diffusion problems. The new condition is essentially the same as the existing one except that the dihedral angles are now measured in a metric depending on the diffusion matrix of the underlying problem. Several variants of the new condition are obtained. Based on one of them, two metric tensors for use in anisotropic mesh generation are developed to account for DMP satisfaction and the combination of DMP satisfaction and mesh adaptivity. Numerical examples are given to demonstrate the features of the linear finite element method for anisotropic meshes generated with the metric tensors.Comment: 34 page

Collisional interaction limits between dark matters and baryons in `cooling flow' clusters

Presuming weak collisional interactions to exchange the kinetic energy between dark matter and baryonic matter in a galaxy cluster, we re-examine the effectiveness of this process in several `cooling flow' galaxy clusters using available X-ray observations and infer an upper limit on the heavy dark matter particle (DMP)$-$proton cross section $\sigma_{\rm xp}$. With a relative collisional velocity $V-$dependent power-law form of $\sigma_{\rm xp}=\sigma_0(V/10^3 {\rm km s^{-1}})^a$ where $a\leq 0$, our inferred upper limit is \sigma_0/m_{\rm x}\lsim 2\times10^{-25} {\rm cm}^2 {\rm GeV}^{-1} with $m_{\rm x}$ being the DMP mass. Based on a simple stability analysis of the thermal energy balance equation, we argue that the mechanism of DMP$-$baryon collisional interactions is unlikely to be a stable nongravitational heating source of intracluster medium (ICM) in inner core regions of `cooling flow' galaxy clusters.Comment: 8 pages, 2 figures, MNRAS accepte

Chemo- and Thermosensory Responsiveness of Grueneberg Ganglion Neurons Relies on Cyclic Guanosine Monophosphate Signaling Elements

Neurons of the Grueneberg ganglion (GG) in the anterior nasal region of mouse pups respond to cool temperatures and to a small set of odorants. While the thermosensory reactivity appears to be mediated by elements of a cyclic guanosine monophosphate (cGMP) cascade, the molecular mechanisms underlying the odor-induced responses are unclear. Since odor-responsive GG cells are endowed with elements of a cGMP pathway, specifically the transmembrane guanylyl cyclase subtype GC-G and the cyclic nucleotide-gated ion channel CNGA3, the possibility was explored whether these cGMP signaling elements may also be involved in chemosensory GG responses. Experiments with transgenic mice deficient for GC-G or CNGA3 revealed that GG responsiveness to given odorants was significantly diminished in these knockout animals. These findings suggest that a cGMP cascade may be important for both olfactory and thermosensory signaling in the GG. However, in contrast to the thermosensory reactivity, which did not decline over time, the chemosensory response underwent adaptation upon extended stimulation, suggesting that the two transduction processes only partially overlap. Copyright (C) 2011 S. Karger AG, Base