New hybrid materials based on the grafting of Pd(II)-amino complexes on the graphitic surface of AC: preparation, structures and catalytic properties

A novel procedure for the preparation of solid Pd(II)-based catalysts consisting of the anchorage of designed Pd(II)-complexes on an activated carbon (AC) surface is reported. Two molecules of the Ar–S–F type (where Ar is a plane-pyrimidine moiety, F a Pd(II)-ligand and S an aliphatic linker) differing in F, were grafted on AC by π–π stacking of the Ar moiety and the graphene planes of the AC, thus favouring the retaining of the metal-complexing ability of F. Adsorption of Pd(II) by the AC/Ar–S–F hybrids occurs via Pd(II)-complexation by F. After deep characterization, the catalytic activities of the AC/Ar–S–F/Pd(II) hybrids on the hydrogenation of 1-octene in methanol as a catalytic test were evaluated. 100% conversion to n-octane at T = 323.1 K and P = 15 bar, was obtained with both catalysts and most of Pd(II) was reduced to Pd(0) nanoparticles, which remained on the AC surface. Reusing the catalysts in three additional cycles reveals that the catalyst bearing the F ligand with a larger Pd-complexing ability showed no loss of activity (100% conversion to n-octane) which is assigned to its larger structural stability. The catalyst with the weaker F ligand underwent a progressive loss of activity (from 100% to 79% in four cycles), due to the constant aggregation of the Pd(0) nanoparticles. Milder conditions, T = 303.1 K and P = 1.5 bar, prevent the aggregation of the Pd(0) nanoparticles in this catalyst allowing the retention of the high catalytic efficiency (100% conversion) in four reaction cycles.

Why firms avoid cutting wages: Survey evidence from European firms. National Bank of Belgium Working Paper No. 251, December 2013

The rarity with which firms reduce nominal wages has been frequently observed, even in the face of considerable negative economic shocks. This paper uses a unique survey of fourteen European countries to ask firms directly about the incidence of wage cuts and to assess the relevance of a range of potential reasons for why they avoid cutting wages. Concerns about the retention of productive staff and a lowering of morale and effort were reported as key reasons for downward wage rigidity across all countries and firm types. Restrictions created by collective bargaining were found to be an important consideration for firms in euro area countries but were one of the lowest ranked obstacles in non-euro area countries. The paper examines how firm characteristics and collective bargaining institutions affect the relevance of each of the common explanations put forward for the infrequency of wage cuts.

Towards a professional army. Changes to the structure of the officer cadre and the manning system of the Russian armed forces. OSW Commentary No. 73, 2012-03-28

The structure of the Russian army’s personnel has undergone a major transformation in recent years. The Armed Forces are no longer a downsized continuation of the Soviet-era mass army, but are gradually becoming a de facto professional army in which conscription, now employed on a diminishing scale, will primarily constitute a first step towards a continued professional military career. The cornerstone for the process of professionalisation has been laid by a personnel reform which cut the number of officer posts by nearly half and considerably restricted the recruitment of new officers, thus restoring traditional proportions to the structure of the officer corps. The plans to ultimately implement a manning system based predominantly on contract service are a natural consequence of these changes. The ongoing professionalisation of the Russian Armed Forces should be treated as a conscious effort which is mainly necessitated by global trends: despite the demographic changes taking place, Russia could still maintain an army with a declared strength of one million soldiers, most of them conscripts.

Role of dietary fibers in the nutritional management of hyperuricemia

Foods rich in adenine and hypoxanthine may contribute to the increase of uricemia. Hyperuricemia is associated with other pathological conditions pertaining to metabolic syndrome. Objective: the assessement of the impact of fiber rich diet on uricemia in patients with metabolic syndrome. Methods: the study involved 46 male patients with metabolic syndrome who claimed to have reduced mobility in fingers, hypertension, obesity, hyperglycemia and hyperuricemia. A validated questionnaire about dietary habits was applied at the beginning of the study and after 6 weeks of fiber-rich diet by eliminating from patients diet preparations of animal food and increased intake of vegetable foods. Blood presure, body mass index, blood glucose and uric acids were measured at the beginning of the study and after 6 weeks of fiber rich diet by daily consumption of 2 servings of added grains - 60g totally and vegetables 200g, fruits 300g respectively. Results: The study shows that at baseline all patients had an inadequate dietary intake of dietary fiber, 28.5 ± 2.2 g/day instead of 38 g per day.The increase in fiber intake of 10 ± 5 g/day was associated with a decrease of serum uric acid by 69.87% from 8.3  0.6 mg/dL to 5.8  0.5 mg/dL, p = 0.008, non-significant decrease of BMI (from 26.8  4.5 to 26.4  4.6 kg/m2, p<0.01), significant decrease of glycemia (from 130  0.8 to 105  4.2mg/dL, p <0.001) and significant decrease in blood pressure (from 150  10.6 to 130  8.4 mmHg, p <0.001). Conclusion: The fiber rich diet decreased blood uric acid, blood glucose levels an arterial pressure in patients with metabolic syndrome.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

Psychology from the standpoint of a behaviorist.

Problems and scope of psychology -- Psychological methods -- The receptors and their stimuli -- Neuro-physiological basis of action -- The organs of response : muscles and glands -- Hereditary modes of response : emotions -- Hereditary modes of response : instinct -- The genesis and retention of explicit bodily habits -- The genesis and retention of explicit and implicit language habits -- The organism at work -- Personality and its disturbance.

Evaluation of a Post Discharge Intervention on 30-Day Re-admission and Emergency Room Use in Patients with Diabetes A Pilot Program

Thesis (Master's)--University of Washington, 2016-06

Mechanisms of B and T lymphocyte accumulation in tumor-draining lymph nodes

Thesis (Master's)--University of Washington, 2016-06

The Renaissance of Performance Funding for Higher Education: Policy Adoption, Implementation, and Impacts

Thesis (Ph.D.)--University of Washington, 2016-06

Sorption and desorption behaviour of acetochlor in surface, subsurface and size-fractionated soil

Pesticides leaching through a soil profile will be exposed to changing environmental sorption and desorption conditions as different horizons with distinct physical and chemical properties are encountered. Soil cores were taken from a clay soil profile and samples taken from 0.0 to 0.3 m (surface), 1.0-1.3 m (mid) and 2.7-3.0 m (deep) and treated with the chloroacetanilide herbicide, acetochlor. Freundlich isotherms revealed that sorption and desorption behaviour varied with each depth sampled. As soil depth increased, the extent and strength of sorption decreased, indicating that the potential for leaching was increased in the subsoils compared with the surface soil. Hysteresis was evident at each of the three depths sampled, although no significant correlations between soil properties and the hysteresis coefficients were evident. Desorption studies using soil fractions with diameters of > 2000, 250-2000, 53-250, 20-53, 2-20, 0-2 and 0-1 mum separated from each of the three soil depths showed that differential desorption kinetics occurred and that the retention of acetochlor significantly correlated (R-2 = 0.998) with organic matter content. A greater understanding of the influence of soil components on the overall sorption and desorption potential of surface and subsurface soils is required to allow accurate prediction of acetochlor retention in the soil. In addition, it is likely that the proportion of each size fraction in a soil horizon would influence acetochlor bioavailability and movement to groundwater.

Application of microencapsulated flavor to extrusion product

Flavoring is still a difficult problem in the snack food industry because of the high volatility of flavors and their instability under extrusion condition. Although postextrusion added flavor is commonly used, it suffers from numerous drawbacks. Flavor losses at the exit die because flash distillation is a critical issue and can only be minimized by controlling the pressure difference at the end of the barrel and the exit die, which, however, affects other desirable product characteristics. Residence time distribution (RTD), as an important intermediate process variable that among others controls the extent of reactions, can also be a major determinant on flavor retention during extrusion. Encapsulation of flavors is a promising alternative to enhance the retention of preextrusion added flavor during extrusion. The capsules should withstand high temperature and shear conditions in, the extruder barrel. Various encapsulation techniques and their encapsulated flavor characteristics are illustrated.

Design of artificial myocardial microtissues

Cultivation technologies promoting organization of mammalian cells in three dimensions are essential for gene-function analyses as well as drug testing and represent the first step toward the design of tissue replacements and bioartificial organs. Embedded in a three-dimensional environment, cells are expected to develop tissue-like higher order intercellular structures (cell-cell contacts, extracellular matrix) that orchestrate cellular functions including proliferation, differentiation, apoptosis, and angiogenesis with unmatched quality. We have refined the hanging drop cultivation technology to pioneer beating heart microtissues derived from pure primary rat and mouse cardiomyocyte cultures as well as mixed populations reflecting the cell type composition of rodent hearts. Phenotypic characterization combined with detailed analysis of muscle-specific cell traits, extracellular matrix components, as well as endogenous vascular endothelial growth factor (VEGF) expression profiles of heart microtissues revealed (1) a linear cell number-microtissue size correlation, (2) intermicrotissue superstructures, (3) retention of key cardiomyocyte-specific cell qualities, (4) a sophisticated extracellular matrix, and (5) a high degree of self-organization exemplified by the tendency of muscle structures to assemble at the periphery of these myocardial spheroids. Furthermore (6), myocardial spheroids support endogenous VEGF expression in a size-dependent manner that will likely promote vascularization of heart microtissues produced from defined cell mixtures as well as support connection to the host vascular system after implantation. As cardiomyocytes are known to be refractory to current transfection technologies we have designed lentivirus-based transduction strategies to lead the way for genetic engineering of myocardial microtissues in a clinical setting.

Sunscreen penetration of human skin and related keratinocyte toxicity after topical application

Sunscreen skin penetration and safety assessment should be considered together in order to ensure that in vitro cytotoxicity studies examine relevant doses of these organic chemical UV filters to which viable epidermal cells are realistically exposed. In this study, we sought to determine whether sufficient topically applied sunscreens penetrated into human viable epidermis to put the local keratinocyte cell populations at risk of toxicity. The penetration and retention of five commonly used sunscreen agents ( avobenzone, octinoxate, octocrylene, oxybenzone and padimate O) in human skin was evaluated after application in mineral oil to isolated human epidermal membranes. Sunscreen concentration - human keratinocyte culture response curves were then defined using changes in cell morphology and proliferation ( DNA synthesis using radiolabelled thymidine uptake studies) as evidence of sunscreens causing toxicity. Following 24 h of human epidermal exposure to sunscreens, detectable amounts of all sunscreens were present in the stratum corneum and viable epidermis, with epidermal penetration most evident with oxybenzone. The concentrations of each sunscreen found in human viable epidermis after topical application, adjusting for skin partitioning and binding effects, were at least 5-fold lower, based on levels detected in viable epidermal cells, than those appearing to cause toxicity in cultured human keratinocytes. It is concluded that the human viable epidermal levels of sunscreens are too low to cause any significant toxicity to the underlying human keratinocytes. Copyright (C) 2005 S. Karger AG, Basel.

The role of disulfide bonds in the structure and function of murine epidermal growth factor (mEGF)

A systematic study using solid phase peptide synthesis has been undertaken to examine the role of the disulfide bonds in the structure and function of mEGF. A combination of one, two and three native disulfide pair analogues of an active truncated (4-48) form of mEGF have been synthesised by replacing specific cysteine residues with isosteric alpha-amino-n-butyric acid (Abu). Oxidation of the peptides was performed using either conventional aerobic oxidation at basic pH, in DMSO under acidic conditions or via selective disulfide formation using orthogonal protection of the cysteine pairs. The contribution of individual, or pairs of, disulfide bonds to EGF structure was evaluated by CD and H-1-NMR spectroscopy. The mitogenic activity of each analogue was determined using Balb/c 3T3 mouse fibroblasts. As we have reported previously (Barnham et al. 1998), the disulfide bond between residues 6 and 20 can be removed with significant retention of biological activity (EC50 20-50 nM). The overall structure of this analogue was similar to that of native mEGF, indicating that the loss of the 6-20 disulfide bridge did not affect the global fold of the molecule. We now show that removal of any other disulfide bond, either singly or in pairs, results in a major disruption of the tertiary structure, and a large loss of activity (EC50>900 nM). Remarkably, the linear analogue appears to have greater activity (EC50 580 nM) than most one and two disulfide bond analogues although it does not have a definable tertiary structure.

Heterozygote effects in mice with partial truncations in the growth hormone receptor cytoplasmic domain: Assessment of growth parameters and phenotype

The GH receptor (GHR) is essential for normal postnatal growth and development, and the molecular basis of GHR action has been studied intensively. Clinical case studies and more recently mouse models have revealed the extensive phenotype of impaired GH action. We recently reported two new mouse models, possessing cytoplasmic truncations at position 569 (plus Y539/545-F) and 391, which were created to identify functional subdomains within the cytoplasmic signaling domain. In the homozygous state, these animals show progressively impaired postnatal growth coupled with complex changes in gene expression. We describe here an extended phenotype analysis encompassing the heterozygote state to identify whether single copies of these mutant receptors bring about partial or dominant-negative phenotypes. It appears that the retention of the ubiquitin-dependent endocytosis motif the N-terminal cytoplasmic domain permits turnover of these mutant receptors because no dominant-negative phenotype is seen. Nonetheless, we do observe partial impairment of postnatal growth in heterozygotes supporting limited haploinsufficiency. Reproductive function is impaired in these models in a progressive manner, in parallel with loss of signal transducer and activator of transcription-5 activation ability. In summary, we describe a more comprehensive phenotypic analysis of these mouse models, encompassing overall and longitudinal body growth, reproductive function, and hormonal status in both the heterozygote and homozygote state. Our results suggest that patients expressing single copies of similarly mutated GHRs would not display an obvious clinical phenotype.