(Table 4+5, Page 290) Distribution of Mn, Fe, Cu. Pb, Zn, Ni and Co in single manganese nodules

Chemical analyses of manganese nodules from the Central Pacific Basin show that their chemical composition varies regionally, although that of the associated sediments is markedly uniform throughout the basin. Mn content varies from 16 to 32% in average. Its higher value is generally found in nodules from siliceous clay and a few from deep-sea clay. Fe content tends to enrich in nodules from deep-sea clay area. Most manganese nodules, except those from deep-sea clay, are remarkably depleted in Fe compared with ones from the other Pacific regions. Mostly, Cu and Ni contents exceed 1% in nodules from siliceous clay, and decrease towards the northwest of the basin where deep-sea clay is distributed. The inter-element relationship between manganese nodules and associated sediments suggests that the mechanism of incorporation of major and minor elements in nodules is apparently different from that of the associated sediments. This finding seems to provide a new interpretation on the problem why manganese nodules having low accumulation rate are not buried by the associated sediments with greater sedimentation rate and then occur on sediment-seawater interface.

(Tables 4-5, page 160) REE contents in ferromanganese concretions from the Gulf of Bothnia and the Barents Sea

Ferromanganese concretions from the Svalbard shelf in the Barents Sea show slightly convex shale-normalized REE patterns with no Eu anomalies. Concretions from the Gulf of Bothnia, northern part of the Baltic Sea, exhibit an enrichment of light REE and negative Eu anomalies. This difference is interpreted as a consequence of different conveyor mechanisms of the REE to the sediment. It is suggested that dissolving biogenic debris contributes to the convex pattern obtained in the Barents Sea, whereas an inorganic suspended fraction with scavenged REE is the main carrier in the Gulf of Bothnia. During oxic diagenesis in the sediment, the scavenged REE are set free into the porewater and contribute to the distribution pattern in concretions found in the Gulf of Bothnia. Small Mn-rich spheroidal concretions are enriched two to five times in REE compared to average shale, whereas Mn-poor flat concretions are low in REE. Specific surface area of the concretion and the depth of burial in the oxidized surface sediment are two factors that strongly affect the enrichment of the REE. Weak Ce anomalies are present in the analysed concretions and a redox level dependence is seen.

A critical review of both the synthesis approach and the receptor profile of the 8-chloro-1-(2′,4′-dichlorophenyl)-N-piperidin-1-yl-1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-c]pyrazole-3-carboxamide and analogue derivatives

We thank European Commission (project “PET BRAIN: Mapping the brain with PET radiolabeled cannabinoid CB1 ligands”; FP7-People-2009-IAPP; Grant Agreement N.25142).

Exploring associations between violent discipline and aggressive behavior in children ages 4-5 in The Republic of Nicaragua: A secondary data analysis of the 2011 Demographic and Health Survey

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

Gender Differences in Early Reading Strategies: a Comparison of Synthetic Phonics Only with a Mixed Approach to Teaching Reading to 4-5 Year-Old Children

A survey of primary schools in England found that girls outperform boys in English across all phases (Ofsted in Moving English forward. Ofsted, Manchester, 2012). The gender gap remains an on-going issue in England, especially for reading attainment. This paper presents evidence of gender differences in learning to read that emerged during the development of a reading scheme for 4- and 5-year-old children in which 372 children from Reception classes in sixteen schools participated in 12-month trials. There were three arms per trial: Intervention non-PD (non-phonically decodable text with mixed methods teaching); Intervention PD (phonically decodable text with mixed methods teaching); and a ‘business as usual’ control condition SP (synthetic phonics and decodable text). Assignment to Intervention condition was randomised. Standardised measures of word reading and comprehension were used. The research provides statistically significant evidence suggesting that boys learn more easily using a mix of whole-word and synthetic phonics approaches. In addition, the evidence indicates that boys learn to read more easily using the natural-style language of ‘real’ books including vocabulary which goes beyond their assumed decoding ability. At post-test, boys using the nonphonically decodable text with mixed methods (Intervention A) were 8 months ahead in reading comprehension compared to boys using a wholly synthetic phonics approach.

Aporte de una actividad f?sica en el mejoramiento de la motricidad gruesa y la detecci?n temprana de su retraso en ni?os de 4-5 a?os

La actividad f?sica es un factor que determina la calidad de vida, el desarrollo motor grueso de los preescolares forma parte fundamental para desarrollarse como seres ?ntegros, es a trav?s del movimiento que los ni?os se conocen a s? mismos y perciben el mundo exterior, el juego permite desarrollar una serie de destrezas y habilidades en los ni?os que logra potencializar su desarrollo. Tomando en consideraci?n la etapa preescolar como eje fundamental debido a que esta etapa permite moldear y perfeccionar los ni?os mediante estimulaciones positivas que contribuyan a desarrollarse de forma normal, actividades como correr, saltar, caminar, nadar, son actividades motoras que desde el nacimiento y a trav?s de la maduraci?n del sistema nervioso central se van adquiriendo y modificando seg?n las demandas del ambiente. Resulta importante que a medida del crecimiento de los ni?os se encuentren siempre en acompa?amiento con sus padres o cuidadores son estos los encargados de permitir la supervivencia del ni?o y brindarle un ?ptimo desarrollo, al ser la primera fuente de socializaci?n estos son los primeros en detectar alg?n retraso en el desarrollo y la importancia de detectarlo a tiempo es utilizar una serie de actividades que eviten y disminuyan esto con la finalidad de que el ni?o alcance todas sus habilidades seg?n el tiempo esperado; la revisi?n te?rica realizada para la presente investigaci?n da cuenta de que la estimulaci?n temprana y la actividad f?sica recreativa(juego) contribuyen positivamente en el desarrollo del ni?o y deben considerarse como una herramienta fundamental en su desarrollo.

6-(4-Aminophenyl)-4,5-dihydro-3(2H)-pyridazinone - An important chemical moiety for development of cardioactive agents: A review

6-(4-Aminophenyl)-4,5-dihydro-3(2H)-pyridazinone moiety is a vital structural part of many cardio-active pyridazinone derivatives which are either in clinical use or have been tested in clinical trials. These include imazodan, CI-930, pimobendan, indolidan, levosimendan, SK&F-93741, Y-590, meribendan, NSP-804, NSP-805, bemoradan, senazodan, amipizone, prinoxodan, SKF 95654, siguazodan and KF 15232. This article briefly reviews relevant literature on various reports on the synthesis and use of this moiety for development of cardio-active agents

Selective Sonogashira Couplings in 1,2,4,5-tetrazine derivatives

1,2,4,5-Tetrazines are six-membered heterocyclic compounds in which the four nitrogen atoms are displayed in a symmetric fashion. Their reactivity is quite different from other heterocyclic aromatic systems due to its unique electron-withdrawing character, comparable to tetra-nitrobenzene. 1 In particular, 1,2,4,5- tetrazines are known to take part in [4+2] inverse-Diels–Alder cycloaddition processes which efficiently lead to the construction of substituted pyridazine systems that are important in drug development and biomarker applications. 2 However, the electronic character of 1,2,4,5-tetrazines hampered the development of 3- ethynyl- and 3,6-diethynyl-1,2,4,5-tetrazine derivatives for molecular electronic applications, proved by the scarcity of examples found in the literature. 3 Herein, we describe the synthesis and characterization of two novel ethynyl-based 1,2,4,5-tetrazine derivatives. Synthesis of 3,6-(4-bromophenyl)-1,2,4,5-tetrazine precursor (1) was achieved in good yield by Pinner’s method, starting from 4-bromobenzonitrile. Despite its low solubility in common organic solvents, this precursor was found to react smoothly under typical Sonogashira coupling conditions to selectively afford the 3-ethynyl (2) and 3,6-diethynyl (3) protected derivatives (Figure 1). Reaction conditions were evaluated in order to provide the best yields and to promote selectivity of the mono- or disubstituted ethynyl derivatives. Finally, deprotection was achieved affording, in the case of compound 3, an unprecedented 3,6- diethynyl-1,2,4,5-tetrazine compound. Time-Dependent Density Functional Theory (TDDFT) calculations for both deprotected ethynyl derivatives were used to simulate electronic spectra. A deep knowledge of the relevant electronic transitions involved and quantitatively satisfactory results of the calculated electronic excitations in comparison with experimental data were obtained.

Effective collision strengths for transitions of Ni XVII

Electron impact excitation collision strengths are required for the analysis and interpretation of stellar observations. This calculation aims to provide fine structure effective collision strengths for the Ni XVII ion using a method which includes contributions from resonances. A DARC calculation has been performed, involving 37 J pi states. The effective collision strengths are calculated by averaging the electron collision strengths over a Maxwellian distribution of electron velocities. The non-zero effective collision strengths for transitions between the fine structure levels are given for electron temperatures (T(e)) in the range log(10) T(e)(K) = 4.5 - 8.5. Data for several transitions from the ground state are discussed in this paper.

New insights into the interactions of serum proteins with bis(maltolato)oxovanadium(IV): Transport and biotransformation of insulin-enhancing vanadium pharmaceuticals

Significant new insights into the interactions of the potent insulin-enhancing compound bis(maltolato)oxovanadium(IV) (BMOV) with the serum proteins, apo-transferrin and albumin, are presented. Identical reaction products are observed by electron paramagnetic resonance (EPR) with either BMOV or vanadyl sulfate (VOSO4) in solutions of human serum apo-transferrin. Further detailed study rules out the presence of a ternary ligand-vanadyl-transferrin complex proposed previously. By contrast, differences in reaction products are observed for the interactions of BMOV and VOSO4 with human serum albumin (HSA), wherein adduct formation between albumin and BMOV is detected. In BMOV-albumin solutions, vanadyl ions are bound in a unique manner not observed in comparable solutions Of VOSO4 and albumin. Presentation of chelated vanadyl ions precludes binding at the numerous nonspecific sites and produces a unique EPR spectrum which is assigned to a BMOV-HSA adduct. The adduct species cannot be produced, however, from a solution Of VOSO4 and HSA titrated with maltol. Addition of maltol to a VOSO4-HSA solution instead results in formation of a different end product which has been assigned as a ternary complex, VO(ma)(HSA). Furthermore, analysis of solution equilibria using a model system of BMOV with 1-methylimidazole (formation constant log K = 4.5(1), by difference electronic absorption spectroscopy) lends support to an adduct binding mode (VO(ma)(2)-HSA) proposed herein for BMOV and HSA. This detailed report of an in vitro reactivity difference between VOSO4 and BMOV may have bearing on the form of active vanadium metabolites delivered to target tissues. Albumin binding of vanadium chelates is seen to have a potentially dramatic effect on pharmacokinetics, transport, and efficacy of these antidiabetic chelates.

Discharge measurements and storm event chemistry at the San Francisco River station (Planta) in 2007-2008

To improve our knowledge of the influence of land-use on solute behaviour and export rates in neotropical montane catchments we investigated total organic carbon (TOC), Ca, Mg, Na, K, NO3 and SO4 concentrations during April 2007-May 2008 at different flow conditions and over time in six forested and pasture-dominated headwaters (0.7-76 km2) in Ecuador. NO3 and SO4 concentrations decreased during the study period, with a continual decrease in NO3 and an abrupt decrease in February 2008 for SO4. We attribute this to changing weather regimes connected to a weakening La Niña event. Stream Na concentration decreased in all catchments, and Mg and Ca concentration decreased in all but the forested catchments during storm flow. Under all land-uses TOC increased at high flows. The differences in solute behaviour during storm flow might be attributed to largely shallow subsurface and surface flow paths in pasture streams on the one hand, and a predominant origin of storm flow from the organic layer in the forested streams on the other hand. Nutrient export rates in the forested streams were comparable to the values found in literature for tropical streams. They amounted to 6-8 kg/ha/y for Ca, 7-8 kg/ha/y for K, 4-5 kg/ha/y for Mg, 11-14 kg/ha/y for Na, 19-22 kg/ha/y for NO3 (i.e. 4.3-5.0 kg/ha/y NO3-N) and 17 kg/ha/y for SO4. Our data contradict the assumption that nutrient export increases with the loss of forest cover. For NO3 we observed a positive correlation of export value and percentage forest cover.

A thermal molecular migration in the solid-state - structures of isomeric 5-amino-4-(2,6-dichlorophenyl)-1-(2-nitrophenyl)-1h-1,2,3-triazole (yellow form i) and 4-(2,6-dichlorophenyl)-5-(2-nitroanilino)-2h-1,2,3-triazole (red form-ii), c14h9cl2n5o2

Yellow form (I): Mr= 350.09, monoclinic, P2Jn, Z--4, a=9.525(1), b=14.762(1), c= 11.268(1),/t, fl= 107.82 (1) o , V= 1508.3 A 3 , Din(flotation in aqueous KI)= 1.539 (2), D x= 1.541 (2) g cm -3, #(Cu Ka, 2 = 1.5418 A) = 40.58 cm -~, F(000) = 712, T= 293 K, R = 8.8% for 2054 significant refections. Red form (II): Mr= 350.09, triclinic, Pi, Z=2, a=9.796(2), b= 10.750 (2), c= 7.421 (1)A, a= 95.29 (2), fl= 0108-2701/84/111901-05501.50 70.18 (1), y = 92-.76 (2) °, V= 731.9 A 3, Din(flotation in KI) = 1.585 (3), D x = 1.588 (3) g cm -3, ~t(Cu Ka, 2 = 1.5418/~) = 40.58 cm -1, F(000) = 356, T=293 K, R = 5.8% for 1866 significant reflections. There are no unusual bond distances or angles. The triazole and two phenyl rings are planar. On the basis of packing considerations the possibility of intermolecular interactions playing a role in the reactivity of the starting material is ruled out.

Crystal structure of (5R,10R)-2,7-dibromo-3,8-dihydroxy-5,10-dimethoxy-5,10-dihydrochromeno[5,4,3-cde]chromene sesquihydrate, C16H12Br2O6 center dot 1.5H(2)O

C16H15Br2O7.5, orthorhombic, P2(1)2(1)2 (no. 18), a = 18.483(2) angstrom, b = 9.413(1) angstrom, c = 10.072(1) angstrom, V = 1752.3 angstrom(3), Z = 4, R-gt(F) = 0.083, wR(ref)(F-2) = 0.202, T= 293 K.