Coordination of the Co2+and Ni2+Ions in Tf2N-Based Ionic Liquids: A Combined X-ray Absorption and Molecular Dynamics Study

Molecular dynamics (MD) simulations and X-ray absorption spectroscopy (XAS) have been combined to study the coordination of the Co2+ and Ni2+ ions in ionic liquids (ILs) based on the bis(trifluoromethylsulfonyl)imide ([Tf2N]-) anion and having different organic cations, namely, 1-butyl-3-methylimidazolium ([C4mim]+), 1,8-bis(3-methylimidazolium-1-yl)octane ([C8(mim)2]2+), N,N,N-trimethyl-N-(2-hydroxyethyl)ammonium ([choline]+), and butyltrimethylammonium ([BTMA]+). Co and Ni K-edge XAS data have been collected on 0.1 mol L-1 Co(Tf2N)2 and Ni(Tf2N)2 solutions and on the metallic salts. MD simulations have been carried out to obtain structural information on the metal ion coordination. The analysis of the extended X-ray absorption fine structure (EXAFS) spectra of the solutions has been carried out based on the atomistic description provided by MD, and the studied ILs have been found to be able to dissolve both the Co(Tf2N)2 and Ni(Tf2N)2 salts giving rise to a different structural arrangement around the metal ions as compared to the solid state. The combined EXAFS and MD results showed that the Co2+ and Ni2+ ions are surrounded by a first solvation shell formed by six [Tf2N]- anions, each coordinating in a monodentate fashion by means of the oxygen atoms. The nature of the IL organic cation has little or no influence on the overall spatial arrangement of the [Tf2N]- anions, so that stable octahedral complexes of the type [M(Tf2N)6]4- (M = Co, Ni) have been observed in all the investigated ILs

Patient characteristics differently affect early cup and stem loosening in THA: a case-control study on 7,535 patients

We postulated that certain patient characteristics have different effects on early THA component loosening. With two matched case-control studies we assessed 3,028 cups and 5,224 stems. Loosening was defined using signs of mechanical component failure on routine follow-up radiographs or revision for aseptic loosening. Women and men had similar cup-loosening odds, but women had lower odds for stem loosening (p < 0.0001). Odds for cup loosening decreased by 2.1% per additional year of age (p = 0.0004), those for stem loosening by 2.4% (p < 0.0001). Each additional kilogram of weight decreased cup loosening odds by 1.3% (p = 0.0051). Each additional unit of BMI increased stem loosening odds (p = 0.0109). Charnley classes B and C were protective factors against loosening of both components. There were no risk differences for the various main diagnoses. Certain patient characteristics differently affected early cup and stem loosening, although some characteristics had the same protective or harmful effect on component surviva

Supply sensitive services in Swiss ambulatory care: An analysis of basic health insurance records for 2003-2007

<p>Abstract</p> <p>Background</p> <p>Swiss ambulatory care is characterized by independent, and primarily practice-based, physicians, receiving fee for service reimbursement. This study analyses supply sensitive services using ambulatory care claims data from mandatory health insurance. A first research question was aimed at the hypothesis that physicians with large patient lists decrease their intensity of services and bill less per patient to health insurance, and vice versa: physicians with smaller patient lists compensate for the lack of patients with additional visits and services. A second research question relates to the fact that several cantons are allowing physicians to directly dispense drugs to patients ('self-dispensation') whereas other cantons restrict such direct sales to emergencies only. This second question was based on the assumption that patterns of rescheduling patients for consultations may differ across channels of dispensing prescription drugs and therefore the hypothesis of different consultation costs in this context was investigated.</p> <p>Methods</p> <p>Complete claims data paid for by mandatory health insurance of all Swiss physicians in own practices were analyzed for the years 2003-2007. Medical specialties were pooled into six main provider types in ambulatory care: primary care, pediatrics, gynecology & obstetrics, psychiatrists, invasive and non-invasive specialists. For each provider type, regression models at the physician level were used to analyze the relationship between the number of patients treated and the total sum of treatment cost reimbursed by mandatory health insurance.</p> <p>Results</p> <p>The results show non-proportional relationships between patient numbers and total sum of treatment cost for all provider types involved implying that treatment costs per patient increase with higher practice size. The related additional costs to the health system are substantial. Regions with self-dispensation had lowest treatment cost for primary care, gynecology, pediatrics and for psychiatrists whereas "prescription only" areas had lowest cost for specialists with non-invasive and invasive activities.</p> <p>Conclusions</p> <p>The results indicate that payment methods for services and for prescription drugs are associated with variations in treatment cost that are unlikely warranted by different medical needs of patients alone. Promoting physician accountability of care by linking reimbursements to quality, not quantity, of services are important policy measures to be considered for health care in Switzerland.</p

Influence of MAX-Phase Deformability on Coating Formation by Cold Spraying

As solid-state deposition technique avoiding oxidation, cold gas spraying is capable of retaining feedstock material properties in the coatings, but typically fails to build up coatings of brittle materials. Ceramic MAX phases show partial deformability in particular lattice directions and may thus successfully deposit in cold spraying. However, deformation mechanisms under high strain rate, as necessary for cohesion and adhesion, are not fully clear yet. A MAX-phase deposit only builds up, if the specific mechanical properties of the MAX phase allow for, and if suitable spray parameter sets get realized. To investigate the influence of material properties and deposition conditions on coating microstructure and quality, three MAX phases, Ti3SiC2, Ti2AlC and Cr2AlC, were selected. Up to ten passes under different spray parameters yielded Ti2AlC and Cr2AlC coatings with thicknesses of about 200-500&nbsp;\ub5m. In contrast, Ti3SiC2 only forms a monolayer, exhibiting brittle laminar failure of the impacting particles. In all cases, the crystallographic structure of the MAX-phase powders was retained in the coatings. Thicker coatings show rather low porosities (&lt; 2%), but some laminar cracks. The deposition behavior is correlated with individual mechanical properties of the different MAX-phase compositions and is discussed regarding the particular, highly anisotropic deformation mechanisms

In vitro characterization of physico-chemical properties, cytotoxicity, bioactivity of urea-crosslinked hyaluronic acid and sodium ascorbyl phosphate nasal powder formulation

An innovative lyophilized dry powder formulation consisting of urea-crosslinked hyaluronic acid (HA-CL) and sodium ascorbyl phosphate (SAP) – LYO HA-CL – SAP- was prepared and characterized in vitro for physico-chemical and biological properties. The aim was to understand if LYO HA-CL – SAP could be used as adjuvant treatment for nasal inflammatory diseases. LYO HA-CL – SAP was suitable for nasal delivery and showed to be not toxic on human nasal septum carcinoma-derived cells (RPMI 2650 cells) at the investigated concentrations. It displayed porous, polygonal particles with unimodal, narrow size distribution, mean geometric diameter of 328.3 ± 27.5 µm, that is appropriate for nasal deposition with no respirable fraction and 88.7% of particles with aerodynamic diameter &gt;14.1 µm. Additionally, the formulation showed wound healing ability on RPMI 2650 cells, and reduced interleukin-8 (IL-8) level in primary nasal epithelial cells pre-induced with lipopolysaccharide (LPS). Transport study across RPMI 2650 cells showed that HA-CL could act not only as carrier for SAP and active ingredient itself, but potentially also as mucoadhesive agent. In conclusion, these results suggest that HA-CL and SAP had anti-inflammatory activity and acted in combination to accelerate wound healing. Therefore, LYO HA-CL – SAP could be a potential adjuvant in nasal anti-inflammatory formulations