Isolation, structure, chemistry, and photochemistry of cis-bis(2,2'-bipyridyl)carbonylchlororuthenium(II) perchlorate

The molecular structure and chemical and photochemical reactions of [Ru(bpy)2(CO)Cl]+ClO4–, which has been isolated from the reaction of ruthenium trichloride and 2,2′-bipyridyl(bpy) in dimethylformamide, are described.

Synthesis, characterization and molecular structure of 1,1′ bis (diphenyl phosphino ferrocene) dioxide complex of the cis-uranyl dichloride

A 1,1' bis(diphenyl phosphino ferrocene) dioxide complex of the uranyl dichloride was synthesized and characterized by elemental analysis, H-1, P-31{H-1} NMR and X-ray diffraction methods. The structure of the compound shows that the uranium(VI) ion is surrounded by four oxygen and two chlorine atoms in an octahedral geometry. Two oxygen atoms from the bis (diphenyl phosphino ferrocene) dioxide and two chlorine atoms form a square planar arrangement. Two uranyl oxygen atoms occupy the axial positions. The bis(diphenyl phosphino ferrocene) dioxide ligand acts as a bidentate chelating ligand with a bite angle of 82.90(16)degrees around the uranyl group. The two chlorine atoms are mutually cis with a CI-U-Cl angle of 97.75(7)degrees.

Cis–trans isomerism in diphenoxido bridged dicopper complexes: role of crystallized water to stabilize the cis isomer, variation in magnetic properties and conversion of both into a trinuclear species

The trans-[Cu2L2Cl2] (1), and cis-[Cu2L2Cl2]·H2O (2) isomers of a diphenoxido bridged Cu2O2 core have been synthesized using a tridentate reduced Schiff base ligand 2-[(2-dimethylamino-ethylamino)-methyl]-phenol. The geometry around Cu(II) is intermediate between square pyramid and trigonal bipyramid (Addison parameter, tau = 0.463) in 1 but nearly square pyramidal (tau = 0.049) in 2. The chloride ions are coordinated to Cu(II) and are trans oriented in 1 but cis oriented in 2. Both isomers have been optimized using density functional theory (DFT) calculations and it is found that the trans isomer is 7.2 kcal mol(-1) more favorable than the cis isomer. However, the hydrogen bonding interaction of crystallized water molecule with chloride ions compensates for the energy difference and stabilizes the cis isomer. Both complexes have been converted to a very rare phenoxido-azido bridged trinuclear species, [Cu3L2(mu(1,1)-N-3)(2)(H2O)(2)(ClO4)(2)] (3) which has also been characterized structurally. All the complexes are antiferromagnetically coupled but the magnitude of the coupling constants are significantly different (J = -156.60, -652.31, and -31.54 cm(-1) for 1, 2, and 3 respectively). Density functional theory (DFT) calculations have also been performed to gain further insight into the qualitative theoretical interpretation on the overall magnetic behavior of the complexes.

Incremental effect of a calcium salt of cis-monounsaturated fatty acids supplement on milk fatty acid composition in cows fed maize silage-based diets

In most Western countries, saturated fatty acid (SFA) intake exceeds recommended levels, which is considered a risk factor for cardiovascular disease (CVD). As milk and dairy products are major contributors to SFA intake in many countries, recent research has focused on sustainable methods of producing milk with a lower saturated fat concentration by altering dairy cow diets. Human intervention studies have shown that CVD risk can be reduced by consuming dairy products with reduced SFA and increased cis-monounsaturated fatty acid (MUFA) concentrations. This milk fatty acid profile can be achieved by supplementing dairy cow diets with cis-MUFA-rich unsaturated oils. However, rumen exposure of unsaturated oils also leads to enhanced milk trans fatty acid (TFA) concentrations. Because of concerns about the effects of TFA consumption on CVD, feeding strategies that increase MUFA concentrations in milk without concomitant increases in TFA concentration are preferred by milk processors. In an attempt to limit TFA production and increase the replacement of SFA by cis-MUFA, a preparation of rumen-protected unsaturated oils was developed using saponification with calcium salts. Four multiparous Holstein-Friesian cows in mid-late lactation were used in a 4 × 4 Latin square design with 21-d periods to investigate the effect of incremental dietary inclusion of a calcium salt of cis-MUFA product (Ca-MUFA; 20, 40, and 60 g/kg of dry matter of a maize silage-based diet), on milk production, composition, and fatty acid concentration. Increasing Ca-MUFA inclusion reduced dry matter intake linearly, but no change was observed in estimated ME intake. No change in milk yield was noted, but milk fat and protein concentrations were linearly reduced. Supplementation with Ca-MUFA resulted in a linear reduction in total SFA (from 71 to 52 g/100 g of fatty acids for control and 60 g/kg of dry matter diets, respectively). In addition, concentrations of both cis- and trans-MUFA were increased with Ca-MUFA inclusion, and increases in other biohydrogenation intermediates in milk fat were also observed. The Ca-MUFA supplement was very effective at reducing milk SFA concentration and increasing cis-MUFA concentrations without incurring any negative effects on milk and milk component yields. However, reduced milk fat and protein concentrations, together with increases in milk TFA concentrations, suggest partial dissociation of the calcium salts in the rumen

A comparative performance analysis of TRMM 3B42 (TMPA) versions 6 and 7 for hydrological applications over Andean-Amazon river basins

The Tropical Rainfall Measuring Mission 3B42 precipitation estimates are widely used in tropical regions for hydrometeorological research. Recently, version 7 of the product was released. Major revisions to the algorithm involve the radar refl ectivity - rainfall rates relationship, surface clutter detection over high terrain, a new reference database for the passive microwave algorithm, and a higher quality gauge analysis product for monthly bias correction. To assess the impacts of the improved algorithm, we compare the version 7 and the older version 6 product with data from 263 rain gauges in and around the northern Peruvian Andes. The region covers humid tropical rainforest, tropical mountains, and arid to humid coastal plains. We and that the version 7 product has a significantly lower bias and an improved representation of the rainfall distribution. We further evaluated the performance of versions 6 and 7 products as forcing data for hydrological modelling, by comparing the simulated and observed daily streamfl ow in 9 nested Amazon river basins. We find that the improvement in the precipitation estimation algorithm translates to an increase in the model Nash-Sutcliffe effciency, and a reduction in the percent bias between the observed and simulated flows by 30 to 95%.

Forests of the tropical eastern Andean flank during the middle pleistocene

Inter-bedded volcanic and organic sediments from Erazo (Ecuador) indicate the presence of four different forest assemblages on the eastern Andean flank during the middle Pleistocene. Radiometric dates (40Ar–39Ar) obtained fromthe volcanic ash indicate that deposition occurred between 620,000 and 192,000 years ago. Examination of the organic sediment composition and the fossil pollen, wood and charcoal it contains provides insight into depositional environment, vegetation assemblage and fire history. The high organic content and abundance of macro fossils found throughout the sediment suggest that during the period of deposition the local environment was either a swamp or a shallow water body. The correlation of fire activity (peaks in charcoal abundance) with volcanic ash deposits through most of the record suggests that volcanoes were the main source of ignition. The low abundance of grass (typically b10%) throughout the sedimentary sequence along with the low abundance of other taxa indicative of open vegetation suggests the persistence of forest at Erazo. Four types of forest assemblage were identified (with the first taxa as the most dominant): i) Alnus-Arecaceae, ii) Miconia- Melastomataceae/Combretaceae-Moraceae/Urticaceae, iii) Arecaceae-Alnus, and iv) Podocarpus with Oreopanax sp. and Melastomataceae/Combretaceae. Changes in the forest floristic composition indicate high vegetation turnover and reassortment of taxa between upper and lower montane forests during the middle Pleistocene as well as the persistence of forest cover.

Response to comment on “The response of vegetation on the Andean flank in western Amazonia to Pleistocene climate change” – M.L. Cárdenas et al., Science 331, 1055 (25 February 2011)”.

Puyasena et al. question our interpretation of climate-driven vegetation change on the Andean flank in western Amazonia during the middle Pleistocene and suggest that the use of Podocarpus spp. as a proxy of past climate change should be reassessed. We defend our assertion that vegetation change at the Erazo study site was predominantly driven by climate change due to concomitant changes recorded by multiple taxa in the fossil record.

The response of vegetation on the Andean flank in western Amazonia to Pleistocene climate change

A reconstruction of past environmental change from Ecuador reveals the response of lower montane forest on the Andean flank in western Amazonia to glacial-interglacial global climate change. Radiometric dating of volcanic ash indicates that deposition occurred ~324,000 to 193,000 years ago during parts of Marine Isotope Stages 9, 7, and 6. Fossil pollen and wood preserved within organic sediments suggest that the composition of the forest altered radically in response to glacial-interglacial climate change. The presence of Podocarpus macrofossils ~1000 meters below the lower limit of their modern distribution indicates a relative cooling of at least 5°C during glacials and persistence of wet conditions. Interglacial deposits contain thermophilic palms suggesting warm and wet climates. Hence, global temperature change can radically alter vegetation communities and biodiversity in this region.

1H-13C HSQC NMR spectroscopy for estimating procyanidin/prodelphinidin and cis/trans-flavan-3-ol ratios of condensed tannin samples: correlation with thiolysis

Studies with a diverse array of 22 purified condensed tannin (CT) samples from nine plant species demonstrated that procyanidin/prodelphinidin (PC/PD) and cis/trans-flavan-3-ol ratios can be appraised by 1H-13C HSQC NMR spectroscopy. The method was developed from samples containing 44 to ~100% CT, PC/PD ratios ranging from 0/100 to 99/1, and cis/trans ratios from 58/42 to 95/5 as determined by thiolysis with benzyl mercaptan. Integration of cross-peak contours of H/C-6' signals from PC and of H/C-2',6' signals from PD yielded nuclei adjusted estimates that were highly correlated with PC/PD ratios obtained by thiolysis (R2 = 0.99). Cis/trans-flavan-3-ol ratios, obtained by integration of the respective H/C-4 cross-peak contours, were also related to determinations made by thiolysis (R2 = 0.89). Overall, 1H-13C HSQC NMR spectroscopy appears to be a viable alternative to thiolysis for estimating PC/PD and cis/trans ratios of CT, if precautions are taken to avoid integration of cross-peak contours of contaminants.

Balanced polymorphism in bottlenecked populations: The case of the CCR5 5 ` cis-regulatory region in Amazonian Amerindians

The 5` cis-regulatory region of the CCR5 gene exhibits a strong signature of balancing selection in several human populations. Here we analyze the polymorphism of this region in Amerindians from Amazonia, who have a complex demographic history, including recent bottlenecks that are known to reduce genetic variability. Amerindians show high nucleotide diversity (pi = 0.27%) and significantly positive Tajima`s D, and carry haplotypes associated with weak and strong gene expression. To evaluate whether these signatures of balancing selection could be explained by demography, we perform neutrality tests based on empiric and simulated data. The observed Tajima`s D was higher than that of other world populations: higher than that found for 18 noncoding regions of South Amerindians, and higher than 99.6% of simulated genealogies, which assume nonequilibrium conditions. Moreover, comparing Amerindians and Asians, the Fst for CCR5 cis-regulatory region was unusually low, in relation to neutral markers. These findings indicate that, despite their complex demographic history, South Amerindians carry a detectable signature of selection on the CCR5 cis-regulatory region. (C) 2010 American Society for Histocompatibility and Immunogenetics. Published by Elsevier Inc. All rights reserved.

Functionally conserved cis-regulatory elements of COL18A1 identified through zebrafish transgenesis

Type XVIII collagen is a component of basement membranes, and expressed prominently in the eye, blood vessels, liver, and the central nervous system. Homozygous mutations in COL18A1 lead to Knobloch Syndrome, characterized by ocular defects and occipital encephalocele. However, relatively little has been described on the role of type XVIII collagen in development, and nothing is known about the regulation of its tissue-specific expression pattern. We have used zebrafish transgenesis to identify and characterize cis-regulatory sequences controlling expression of the human gene. Candidate enhancers were selected from non-coding sequence associated with COL18A1 based on sequence conservation among mammals. Although these displayed no overt conservation with orthologous zebrafish sequences, four regions nonetheless acted as tissue-specific transcriptional enhancers in the zebrafish embryo, and together recapitulated the major aspects of col18a1 expression. Additional post-hoc computational analysis on positive enhancer sequences revealed alignments between mammalian and teleost sequences, which we hypothesize predict the corresponding zebrafish enhancers; for one of these, we demonstrate functional overlap with the orthologous human enhancer sequence. Our results provide important insight into the biological function and regulation of COL18A1, and point to additional sequences that may contribute to complex diseases involving COL18A1. More generally, we show that combining functional data with targeted analyses for phylogenetic conservation can reveal conserved cis-regulatory elements in the large number of cases where computational alignment alone falls short. (C) 2009 Elsevier Inc. All rights reserved.

Modulation of rat neutrophil function in vitro by cis- and trans-MUFA

In the present study, the effects of trans-MUFA, elaidic acid (EA; 18 : 1-9t) and vaccenic acid (VA; 18 : 1-11t) on rat neutrophil functions were compared with those of cis-monounsaturated oleic acid (OA) (18 : 1-9c) and saturated stearic acid (SA; 18 : 0) (10-150 mu M). Trans-fatty acids enhanced neutrophil phagocytic capacity, superoxide (O(2)(center dot-)) and hydrogen peroxide production, and candidacidal activity. The same effects were observed for OA. Cells treated with trans-MUFA showed reduced production of NO(center dot), whereas those treated with OA showed an increase in production. Treatment with SA did not provoke significant effect on the parameters investigated. The increase in O(2)(center dot-) production induced by MUFA was not observed when diphenyleneiodonium, an NADPH oxidase inhibitor, was added to the medium. This finding suggests that MUFA stimulate neutrophil NADPH oxidase activity. The addition of 3-[1-[3-(dimethylamino)propyl]-1H-indol-3-yl]-4-(1H-inclol-3-yl)-1H-pyrrole-2,5-dione, a protein kinase C (PKC) inhibitor, and wortmannin, a phosphatidylinositol-3 kinase (PI3K) inhibitor, did not affect O(2)(center dot-) production induced by MUFA. Therefore, the mechanisms by which MUFA stimulate NADPH oxidase are not dependent on PKC and do not seem to involve PI3K. Experiments using Zn(2+), an inhibitor of NADPH oxidase H(+) channel, indicated that MUFA activate the NADPH oxidase complex in rat neutrophil due to opening of H(+) channel.