Negative effective Li transference numbers in Li salt/ionic liquid mixtures: does Li drift in the "Wrong" direction?

The electrophoretic mobilities µ of all ion species in the lithium salt/ionic liquid mixtures LiTFSA/EmimTFSA and LiBF4/EmimBF4 are determined by 1H, 19F and 7Li electrophoretic NMR. The average drift direction of Li is identical to that of the anions TFSA- or BF4-. This proves a correlated ion motion of Li with the anions in negatively charged Li-containing clusters in both systems. The effective charge of these clusters is determined as -1, or -2 in the system with TFSA or BF4, respectively, pointing at the existence of [Li(TFSA)2]- or [Li(BF4)3]2-. This behavior is described by a negative effective transference number of Li, resulting in a negative contribution of Li ions to the overall conductivity. Li effective transference numbers are in the range of -0.04 to -0.02, depending on Li salt concentration and anion type. Transference numbers thus clearly deviate from apparent transference numbers estimated from diffusion coefficients, as an effect of a vehicular transport mechanism. This has important implications for the mechanism of Li mass transport in Li ion batteries as the drift of charged clusters has to be overcompensated by diffusive mass transport of neutral, Li-containing aggregates.

Spin relaxation studies of Li+ ion dynamics in polymer gel electrolytes.

Two ternary polymer gel electrolyte systems are compared, containing either polyethylene oxide (PEO) or the poly-ionic liquid poly(diallyldimethylammonium) bis(trifluoromethyl sulfonyl)imide (PDADMA-TFSI). Both gel types are based on the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethyl sulfonyl)imide (P14TFSI) and LiTFSI. We study the influence of the polymers on the local lithium ion dynamics at different polymer concentrations using 7Li spin-lattice relaxation data in dependence on frequency and temperature. In all cases the relaxation rates are well described by the Cole-Davidson motional model with Arrhenius dependence of the correlation time and a temperature dependent quadrupole coupling constant. For both polymers the correlation times are found to increase with polymer concentration. The activation energy of local motions slightly increases with increasing PEO concentration, and slightly decreases with increasing PDADMA-TFSI concentration. Thus the local Li+ motion is reduced by the presence of either polymer; however, the reduction is less effective in the PDADMA+ samples. We thus conclude that mechanical stabilization of a liquid electrolyte by a polymer can be achieved at a lower decrease of Li+ motion when a cationic polymer is used instead of PEO.

Vasculoprotective properties of the endothelial glycocalyx: effects of fluid shear stress.

The endothelial glycocalyx exerts a wide array of vasculoprotective effects via inhibition of coagulation and leucocyte adhesion, by contributing to the vascular permeability barrier and by mediating shear stress-induced NO release. In this review, we will focus on the relationship between fluid shear stress and the endothelial glycocalyx. We will address the hypothesis that modulation of glycocalyx synthesis by fluid shear stress may contribute to thinner glycocalyces, and therefore more vulnerable endothelium, at lesion-prone sites of arterial bifurcations. Finally, we will discuss the effects of known atherogenic stimuli such as hyperglycaemia on whole body glycocalyx volume in humans and its effect on endothelial function.

An investigation into the role of oxygen free radical scavengers in preventing polymethylmethacrylate-induced necrosis in an osteoblast cell culture.

This study examined the effect of polymethylmethacrylate (PMMA) on osteocytic necrosis and the role of free radical scavengers in minimizing this damage. Bovine osteoblast cells with a characteristic phenotype were seeded at a density of 4x10(4) cells/cm2 and cultured in a DMEM supplemented with 10% fetal calf serum. A transwell insert with 2 cc of PMMA was suspended above the culture, and a time log response curve was established following elusion of free radicals around the osteoblast media. Chemiluminescence was used to determine quantitative free radical release. Using a Student's two-tailed t test there was a significant difference in the amount of hydroxyl radical released at 1-6 hours compared with controls (P=.028). Using histologic markers, there was a significant correlation between the use of PMMA and osteoblast cell necrosis. Transwell plates were coated with varying concentrations of mannitol, a known hydroxyl radical scavenger. A log dose response curve was established. There was a clear statistical association between a 10% mannitol solution and a reduction in the free radical release from PMMA (P=.03). Similarly, using Trypan blue histologic staining, there was a significant reduction in PMMA-induced cell necrosis when 10% mannitol was used as a scavenger (P=.01). A Rockwell superficial hardness test was used to determine whether mannitol had any effect on the surface hardness of the polymer. No statistical difference could be found between those treated with mannitol and controls at a depth of up to 1 mm. These results demonstrate hydroxyl radical is released from the polymerization reaction of PMMA. These radicals cause cell death in an osteoblast culture medium. This has been addressed using a 10% mannitol solution, which reduced cell necrosis.

Learning leadership: students' experiences of a midwifery mentoring practicum.

A leadership mentoring practicum is described wherein nurse-midwifery students are placed with leader/mentors at the state, regional, and national levels of organizations. Logs are kept by the students and discussions at student-faculty seminars focus on linking leadership theory to observations of leadership qualities and behaviours in the mentors. A profile of a "composite leader" derived from the students' experience experiences is presented.

Enamel specific protein kinases and state of phosphorylation of purified amelogenins.

Ameloblastic tissue samples from unerupted bone molars were used to prepare subcellular enamel protein kinase preparations, nuclear + plasma membrane, cytosolic and microsomal, and used in in vitro phosphorylation of purified 20 kDa bovine amelogenin in the presence of 32P-ATP. Both cytosolic and microsomal preparations can phosphorylate purified native amelogenins, the addition of Ca2+ slightly increased the microsomal enzyme activity or at least did not inhibit the activity, whereas the presence of Ca2+ substantially decreased the cytosolic kinase activity towards phosphorylation of amelogenins. A comparative analysis using the enamel microsomal kinase against osteopontin, dephosphorylated casein and bone sialoprotein showed no phosphorylation of the first two proteins, and only minor phosphorylation of the bone sialoprotein. Overall, the present work demonstrates for the first time that the protein kinase responsible for the phosphorylation of amelogenins is a novel kinase, which is not inhibited by Ca2+, unlike the microsomal protein kinase (casein kinase type-II) of bone which phosphorylates secretory proteins osteopontin and bone sialoprotein and is strongly CaZ+ inhibited. The direct phosphoserine analysis on the purified bovine 20 kDa amelogenin indicated the presence of 0.8 moles of phosphoserine/mole protein naturally occurring, consistent with the quantitative analysis of 14C-radiolabeling of phosphoserines by conversion to dehydroalanine and in situ reaction with the thiol agent, 14C-mercaptoethanol, 0.64 moles 14C-incorporated/mole 20 kDa amelogenin. The purified low Mramelogenins 5.3 kDa E4 (TRAP) and 7.2 kDa E3 (LRAP), were also derivatized by 14C-mercaptoethanol, providing 0.46 and 0.88 moles 14C-incorporated/mole respectively. Further studies of the 14C-radiolabeled E4 amelogenin by sequence analysis confirmed one site of label to be at position 16 from the N-terminal and hence provided a direct evidence for the naturally occurring phosphoserine residue at this position.