Cycloadditions of chiral carbonyl ylides with imine dipolarophiles as a route to enantiomerically pure alpha-amino-beta-hydroxy acids

The preparation of enantiomerically pure threo-beta-amino-alpha-hydroxy acids via 1,3-dipolar cycloadditions of imine dipolarophiles with the chiral isomunchnone derived from (5R)-5-phenylmorpholin-3-one 1 is described. The cycloadducts were obtained with excellent diastereofacial- and exo-selectivity. Subsequent hydrolysis and chemoselective exocyclic amide cleavage afforded the threo-beta-amino-alpha-hydroxy acids with recovery of the initial chiral auxiliary. (C) 2009 Published by Elsevier Ltd.

A stable pure hydroxyl layer on Pt{110}-(1x2)

The adsorption of water and coadsorption with oxygen on the missing-row reconstructed Pt{110}-(1x2) surface was studied by using temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy. Coadsorbed oxygen below saturation (<0.65 +/- 0.05 ML) leads to the formation of 014, which occupies sites near the ridge Pt atoms, In contrast to the more closely packed Pt{111} Surface, OH appears not to form hydrogen bonds with coadsorbed water molecules and is stable after the desorption of water tip to about 205 K (as determined by TPD). Because OH and atomic oxygen compete for adsorption sites, water dissociation is only observed for oxygen coverages below saturation. In the absence of coadsorbed oxygen, water stays intact at all temperatures and forms a strongly bound layer of 2 ML coverage oil the clean Pt{110}-(1x2) surface at temperatures between 140 and 175 K.

Multi-microprocessor control of processes with pure time delay

In 1967 a novel scheme was proposed for controlling processes with large pure time delay (Fellgett et al, 1967) and some of the constituent parts of the scheme were investigated (Swann, 1970; Atkinson et al, 1973). At that time the available computational facilities were inadequate for the scheme to be implemented practically, but with the advent of modern microcomputers the scheme becomes feasible. This paper describes recent work (Mitchell, 1987) in implementing the scheme in a new multi-microprocessor configuration and shows the improved performance it provides compared with conventional three-term controllers.

Efficiency and purity control in the preparation of pure and/or aluminum-doped barium ferrites by hydrothermal methods using ferrous ions as reactants

The synthesis of hexagonal barium ferrite (BaFe12O19) was studied under hydrothermal conditions by a method in which a significant amount of ferrous chloride was introduced along side ferric chloride among the starting materials. Though all of the Fe2+ ions in the starting material were converted to Fe3+ ions in the final product, Fe2+ was confirmed to participate differently from the Fe3+ used in the conventional method in the mechanism of forming barium ferrite. Indeed the efficiency of the synthesis and the quality of the product and the lack of impurities such as Fe2O3 and BaFe2O4 were improved when Fe2+ was included. However, the amount of ferrous ions that could be included to obtain the desired product was limited with an optimum ratio of 2:8 for FeCl2/FeCl3 when only 2h of reaction time were needed. It was also found that the role of trivalent Fe3+ could be successfully replaced by Al3+. Up to 50% of their on could be replaced by Al3+ in the reactants to produce Al- doped products. It was also found that the ratio of Fe2+/M3+ could be increased in the presence of Al3+ to produce high quality barium ferrite.

Synthesis and X-ray crystal structure of the triethylammonium magnesium β-octamolybdate(VI)salt[Et3NH]2[Mg(H2O)6Mo8O26]·2H2O

[Et3NH]4[Mo8O26] reacted with MgCl2 giving the triethylammonum magnesium β-octamolybdate(VI) salt [Et3NH]2[Mg(H2O)6Mo8O26]·2H2O (3) and the triethylammonium hydronium β-octaamolybdate(VI) salt [Et3NH]3[(H3O)Mo8O26·2H2O (4), respectively. A small amount of [Et3NH]2[Mo6O269] was formed as a by-product. The salts 3 and 4 were characterized by X-ray crystallography. The [Mg(H2O)6Mo8O26]2− moiety in 3 is polymeric, with each octahedral [Mg(H2O)6]2+ ion sandwiched between two β[Mo8O26]4− ions, being hydrogen bonded to three terminal MOO oxygen atoms on one face of each β[Mo8O26]4− ion. The X-ray crystal structure of 4 corresponds to the reported previously. IR and conductivity data are given for 3 and 4.

Dietary levels of pure flavonoids improve spatial memory performance and increase hippocampal brain-derived neurotrophic factor.

Evidence suggests that flavonoid-rich foods are capable of inducing improvements in memory and cognition in animals and humans. However, there is a lack of clarity concerning whether flavonoids are the causal agents in inducing such behavioral responses. Here we show that supplementation with pure anthocyanins or pure flavanols for 6 weeks, at levels similar to that found in blueberry (2% w/w), results in an enhancement of spatial memory in 18 month old rats. Pure flavanols and pure anthocyanins were observed to induce significant improvements in spatial working memory (p = 0.002 and p = 0.006 respectively), to a similar extent to that following blueberry supplementation (p = 0.002). These behavioral changes were paralleled by increases in hippocampal brain-derived neurotrophic factor (R = 0.46, p<0.01), suggesting a common mechanism for the enhancement of memory. However, unlike protein levels of BDNF, the regional enhancement of BDNF mRNA expression in the hippocampus appeared to be predominantly enhanced by anthocyanins. Our data support the claim that flavonoids are likely causal agents in mediating the cognitive effects of flavonoid-rich foods.

Shoot calcium and magnesium concentrations differ between subtaxa, are highly heritable, and associate with potentially pleiotropic loci in Brassica oleracea

Calcium (Ca) and magnesium (Mg) are the most abundant group II elements in both plants and animals. Genetic variation in shoot Ca and shoot Mg concentration (shoot Ca and Mg) in plants can be exploited to biofortify food crops and thereby increase dietary Ca and Mg intake for humans and livestock. We present a comprehensive analysis of within-species genetic variation for shoot Ca and Mg, demonstrating that shoot mineral concentration differs significantly between subtaxa (varietas). We established a structured diversity foundation set of 376 accessions to capture a high proportion of species-wide allelic diversity within domesticated Brassica oleracea, including representation of wild relatives (C genome, 1n = 9) from natural populations. These accessions and 74 modern F-1 hybrid cultivars were grown in glasshouse and field environments. Shoot Ca and Mg varied 2- and 2.3-fold, respectively, and was typically not inversely correlated with shoot biomass, within most subtaxa. The closely related capitata (cabbage) and sabauda (Savoy cabbage) subtaxa consistently had the highest mean shoot Ca and Mg. Shoot Ca and Mg in glasshouse-grown plants was highly correlated with data from the field. To understand and dissect the genetic basis of variation in shoot Ca and Mg, we studied homozygous lines from a segregating B. oleracea mapping population. Shoot Ca and Mg was highly heritable (up to 40). Quantitative trait loci (QTL) for shoot Ca and Mg were detected on chromosomes C2, C6, C7, C8, and, in particular, C9, where QTL accounted for 14 to 55 of the total genetic variance. The presence of QTL on C9 was substantiated by scoring recurrent backcross substitution lines, derived from the same parents. This also greatly increased the map resolution, with strong evidence that a 4-cM region on C9 influences shoot Ca. This region corresponds to a 0.41-Mb region on Arabidopsis (Arabidopsis thaliana) chromosome 5 that includes 106 genes. There is also evidence that pleiotropic loci on C8 and C9 affect shoot Ca and Mg. Map-based cloning of these loci will reveal how shoot-level phenotypes relate to Ca 21 and Mg 21 uptake and homeostasis at the molecular level.

Distribution of calcium (Ca) and magnesium (Mg) in the leaves of Brassica rapa under varying exogenous Ca and Mg supply

Background and Aims Leafy vegetable Brassica crops are an important source of dietary calcium (Ca) and magnesium (Mg) and represent potential targets for increasing leaf Ca and Mg concentrations through agronomy or breeding. Although the internal distribution of Ca and Mg within leaves affects the accumulation of these elements, such data are not available for Brassica. The aim of this study was to characterize the internal distribution of Ca and Mg in the leaves of a vegetable Brassica and to determine the effects of altered exogenous Ca and Mg supply on this distribution. Methods Brassica rapa ssp. trilocularis ‘R-o-18’ was grown at four different Ca:Mg treatments for 21 d in a controlled environment. Concentrations of Ca and Mg were determined in fully expanded leaves using inductively coupled plasma-mass spectrometry (ICP-MS). Internal distributions of Ca and Mg were determined in transverse leaf sections at the base and apex of leaves using energy-dispersive X-ray spectroscopy (EDS) with cryo-scanning electron microscopy (cryo-SEM). Key Results Leaf Ca and Mg concentrations were greatest in palisade and spongy mesophyll cells, respectively, although this was dependent on exogenous supply. Calcium accumulation in palisade mesophyll cells was enhanced slightly under high Mg supply; in contrast, Mg accumulation in spongy mesophyll cells was not affected by Ca supply. Conclusions The results are consistent with Arabidopsis thaliana and other Brassicaceae, providing phenotypic evidence that conserved mechanisms regulate leaf Ca and Mg distribution at a cellular scale. The future study of Arabidopsis gene orthologues in mutants of this reference B. rapa genotype will improve our understanding of Ca and Mg homeostasis in plants and may provide a model-to-crop translation pathway for targeted breeding.

Comparative analysis of performance and stability among composite cross populations, variety mixtures and pure lines of winter wheat in organic and conventional cropping systems

This study investigated the effects of increased genetic diversity in winter wheat (Triticum aestivum L.), either from hybridization across genotypes or from physical mixing of lines, on grain yield, grain quality, and yield stability in different cropping environments. Sets of pure lines (no diversity), chosen for high yielding ability or high quality, were compared with line mixtures (intermediate level of diversity), and lines crossed with each other in composite cross populations (CCPn, high diversity). Additional populations containing male sterility genes (CCPms) to increase outcrossing rates were also tested. Grain yield, grain protein content, and protein yield were measured at four sites (two organically-managed and two conventionally-managed) over three years, using seed harvested locally in each preceding year. CCPn and mixtures out-yielded the mean of the parents by 2.4% and 3.6%, respectively. These yield differences were consistent across genetic backgrounds but partly inconsistent across cropping environments and years. Yield stability measured by environmental variance was higher in CCPn and CCPms than the mean of the parents. An index of yield reliability tended to be higher in CCPn, CCPms and mixtures than the mean of the parents. Lin and Binns’ superiority values of yield and protein yield were consistently and significantly lower (i.e. better) in the CCPs than in the mean of the parents, but not different between CCPs and mixtures. However, CCPs showed greater early ground cover and plant height than mixtures. When compared with the (locally non-predictable) best-yielding pure line, CCPs and mixtures exhibited lower mean yield and somewhat lower yield reliability but comparable superiority values. Thus, establishing CCPs from smaller sets of high-performing parent lines might optimize their yielding ability. On the whole, the results demonstrate that using increased within-crop genetic diversity can produce wheat crops with improved yield stability and good yield reliability across variable and unpredictable cropping environments.

Comparative analysis of the fit of 3-unit implant-supported frameworks cast in nickel-chromium and cobalt-chromium alloys and commercially pure titanium after casting, laser welding, and simulated porcelain firings

This study compared the vertical misfit of 3-unit implant-supported nickel-chromium (Ni-Cr) and cobalt-chromium (Co-Cr) alloy and commercially pure titanium (cpTi) frameworks after casting as 1 piece, after sectioning and laser welding, and after simulated porcelain firings. The results on the tightened side showed no statistically significant differences. On the opposite side, statistically significant differences were found for Co-Cr alloy (118.64 mu m [SD: 91.48] to 39.90 mu m [SD: 27.13]) and cpTi (118.56 mu m [51.35] to 27.87 mu m [12.71]) when comparing 1-piece to laser-welded frameworks. With both sides tightened, only Co-Cr alloy showed statistically significant differences after laser welding. Ni-Cr alloy showed the lowest misfit values, though the differences were not statistically significantly different. Simulated porcelain firings revealed no significant differences.

Tensile bond strength of cast commercially pure titanium and cast gold-alloy posts and cores cemented with two luting agents

Statement of problem. In vitro studies on the retentive strengths of various cements used to retain posts have reported conflicting results. Purpose. The purpose of this study was to compare the tensile strength of commercially pure titanium and type III cast gold-alloy posts and cores cemented with zinc phosphate or resin cement. Material and methods. Forty-two extracted human canines were endoclontically treated. The root preparations were accomplished using Largo reamers (10 mm in depth and 1.7 mm in diameter). Acrylic resin patterns for the posts and cores were made, and specimens were cast in commercially pure titanium and in type III gold alloy (n=7). Fourteen titanium cast posts and cores were submitted to surface treatment with Kroll acid solution and to scanning electron microscopy (SEM), before and after acid etching. The groups (n=7) were cemented with zinc phosphate cement or resin cement (Panavia F). Tensile strengths were measured in a universal testing machine at a crosshead speed of 0.5 mm/min. The results (Kgf) were statistically analyzed by 2-way ANCIVA (alpha=.05). Results. The 2-way ANOVA indicated that there were no significant differences among the groups tested. Retentive means for zinc phosphate and Panavia F cements were statistically similar. The bond strength was not Influenced by the alloy, the luting material, or the etching treatment. SEM analysis indicated that the etched surfaces were smoother than those that did not receive surface treatment, but this fact did not influence the results. Conclusions. Commercially pure titanium cast posts and cores cemented with zinc phosphate and resin cements demonstrated similar mean tensile retentive values. Retentive values were also similar to mean values recorded for cast gold-alloy posts and cores cemented with zinc phosphate cement and resin cements.