Structural variations in self-assembled coordination complexes of Zn(II) with hexamethylenetetramine and isomeric 2-, 3- and 4-nitrobenzoates

Three new zinc(II)-hexamethylenetetramine (hmt) complexes [Zn-2(4-nbz)(4)(mu(2)-hmt)(OH2)(hmt)] (1). [Zn-2(2-nbz)(4)(mu(2)-hmt)(2)](n) (2) and [Zn-3(3-nbz)(4)(mu(2)-hmt)(mu(2)-OH)(mu(3)-OH)](n) (3) with three isomeric nitrobenzoate, [4-nbz = 4-nitrobenzoate, 2-nbz = 2-nitrobenzoate and 3-nbz = 3-nitrobenzoate] have been synthesized and structurally characterized by X-ray crystallography. Their identities have also been established by elemental analysis: IR, NMR, UV-Vis and mass spectral studies. 1 is a dinuclear complex formed by bridging hmt with mu(2) coordinating mode. The geometry around the Zn centers in 1 is distorted tetrahedral. Paddle-wheel centrosymmetric Zn-2(2-nbz)(4) units of complex 2 are interconnected by mu(2)-hmt forming a one-dimensional chain with square-pyramidal geometries around the Zn centers. Compound 3 contains a mu(2)/mu(3)-hydroxido and mu(2)-hmt bridged 1D chain. In this complex, varied geometries around the Zn centers are observed viz, tetrahedral, square pyramidal and trigonal bipyramidal. Various weak forces, i.e. lone pair-pi, pi-pi and CH-pi interactions, play a key role in stabilizing the observed structures for complexes 1,2 and 3. This series of complexes demonstrates that although the nitro group does not coordinate to the metal center, its presence at the 2-, 3- or 4-position of the phenyl ring has a striking effect on the dimensionality as well as the structure of the resulted coordination polymers, probably due to the participation of the nitro group in 1.p.center dot center dot center dot pi and/or C-H center dot center dot center dot pi interactions.

Complexes of NiX2 (X=Cl− and NO3−) with a NNO donor Schiff base: anion dependent structural variations and spectroscopic behaviour

Two new nickel(11) complexes, [NiLL'(H2O)(2)Cl] (1) and [{NiLL'(H2O)](2)(mu-H)]NO3·H2O(2), have been synthesized using a tridentate Schiff base ligand, HL, 2-[(2-dimethylamino-ethylimino)-methyl]-phenol, along with Cl- or NO3(-) as an anionic co-ligand or counter anion (where L'H = salicylaldehyde). Both complexes have been characterized by X-ray crystallography. The structural analyses reveal that complex 1 is mononuclear whereas 2 is a hydrogen-bridged dinuclear complex. The Ni(II) ions possess a distorted octahedral geometry in both structures. Both complexes show negative solvatochromic behaviour with increasing donor number (DN) of the solvent. In more coordinating solvents, like DMSO or methanol, the colour of the solutions is green, whereas in less coordinating solvents, like dichloromethane (DCM) or acetonitrile, it is red.

Indian summer monsoon variations could have affected the early Holocene woodland expansion in the Near East

Postglacial expansion of deciduous oak woodlands of the Zagros—Anti-Taurus Mountains, a major biome of the Near East, was delayed until the middle Holocene at ~6300 cal. yr BP. The current hypotheses explain this delay as a consequence of a regional aridity during the early Holocene, slow migration rates of forest trees, and/or a long history of land use and agro-pastoralism in this region. In the present paper, support is given to a hypothesis that suggests different precipitation seasonalities during the early Holocene compared with the late Holocene. The oak species of the Zagros—Anti-Taurus Mts, particularly Quercus brantii Lindl., are strongly dependent on spring precipitation for regeneration and are sensitive to a long dry season. Detailed analysis of modern atmospheric circulation patterns in SW Asia during the late spring suggests that the Indian Summer Monsoon (ISM) intensification can modify the amount of late spring and/or early summer rainfall in western/northwestern Iran and eastern Anatolia, which could in turn have controlled the development of the Zagros—Anti-Taurus deciduous oak woodlands. During the early Holocene, the northwestward shift of the Inter-Tropical Convergence Zone (ITCZ) could have displaced the subtropical anticyclonic belt or associated high pressure ridges to the northwest. The latter could, in turn, have prevented the southeastward penetration of low pressure systems originating from the North Atlantic and Black Sea regions. Such atmospheric configuration could have reduced or eliminated the spring precipitation creating a typical Mediterranean continental climate characterized by winter-dominated precipitation. This scenario highlights the complexity of biome response to climate system interactions in transitional climatic and biogeographical regions.

Simulated variations in atmospheric CO2 over a Wisconsin forest using a coupled ecosystem-atmosphere model

Ecosystem fluxes of energy, water, and CO2 result in spatial and temporal variations in atmospheric properties. In principle, these variations can be used to quantify the fluxes through inverse modelling of atmospheric transport, and can improve the understanding of processes and falsifiability of models. We investigated the influence of ecosystem fluxes on atmospheric CO2 in the vicinity of the WLEF-TV tower in Wisconsin using an ecophysiological model (Simple Biosphere, SiB2) coupled to an atmospheric model (Regional Atmospheric Modelling System). Model parameters were specified from satellite imagery and soil texture data. In a companion paper, simulated fluxes in the immediate tower vicinity have been compared to eddy covariance fluxes measured at the tower, with meteorology specified from tower sensors. Results were encouraging with respect to the ability of the model to capture observed diurnal cycles of fluxes. Here, the effects of fluxes in the tower footprint were also investigated by coupling SiB2 to a high-resolution atmospheric simulation, so that the model physiology could affect the meteorological environment. These experiments were successful in reproducing observed fluxes and concentration gradients during the day and at night, but revealed problems during transitions at sunrise and sunset that appear to be related to the canopy radiation parameterization in SiB2.

Electrical signature in polar night cloud base variations

Layer clouds are globally extensive. Their lower edges are charged negatively by the fair weather atmospheric electricity current flowing vertically through them. Using polar winter surface meteorological data from Sodankyla ̈ (Finland) and Halley (Antarctica), we find that when meteorological diurnal variations are weak, an appreciable diurnal cycle, on average, persists in the cloud base heights, detected using a laser ceilometer. The diurnal cloud base heights from both sites correlate more closely with the Carnegie curve of global atmospheric electricity than with local meteorological measurements. The cloud base sensitivities are indistinguishable between the northern and southern hemispheres, averaging a (4.0 ± 0.5) m rise for a 1% change in the fair weather electric current density. This suggests that the global fair weather current, which is affected by space weather, cosmic rays and the El Nin ̃o Southern Oscillation, is linked with layer cloud properties.

Summertime total ozone variations over middle and polar latitudes

The statistical relationship between springtime and summertime ozone over middle and polar latitudes is analyzed using zonally averaged total ozone data. Shortterm variations in springtime midlatitude ozone demonstrate only a modest correlation with springtime polar ozone variations. However by early summer, ozone variations throughout the extratropics are highly correlated. Analysis of correlation functions indicates that springtime midlatitude ozone, not polar ozone, is the best predictor for summertime polar ozone. Long-term total ozone trends at middle and high latitudes are also different for spring and nearly identical for summer. About 39% of the observed southern midlatitude ozone decline in December can be attributed to the polar ozone depletion up to November. In the Northern Hemisphere, the corresponding contribution is about 15%, but the error bars are too large to make an accurate estimate.

The influence of anthropogenic aerosol on multi-decadal variations of historical global climate

Analysis of single forcing runs from CMIP5 (the fifth Coupled Model Intercomparison Project) simulations shows that the mid-twentieth century temperature hiatus, and the coincident decrease in precipitation, is likely to have been influenced strongly by anthropogenic aerosol forcing. Models that include a representation of the indirect effect of aerosol better reproduce inter-decadal variability in historical global-mean near-surface temperatures, particularly the cooling in the 1950s and 1960s, compared to models with representation of the aerosol direct effect only. Models with the indirect effect also show a more pronounced decrease in precipitation during this period, which is in better agreement with observations, and greater inter-decadal variability in the inter-hemispheric temperature difference. This study demonstrates the importance of representing aerosols, and their indirect effects, in general circulation models, and suggests that inter-model diversity in aerosol burden and representation of aerosol–cloud interaction can produce substantial variation in simulations of climate variability on multi decadal timescales.

Sequential variations of phytoplankton growth and mortality in an NPZ model: a remote-sensing-based assessment

Radiometric data in the visible domain acquired by satellite remote sensing have proven to be powerful for monitoring the states of the ocean, both physical and biological. With the help of these data it is possible to understand certain variations in biological responses of marine phytoplankton on ecological time scales. Here, we implement a sequential data-assimilation technique to estimate from a conventional nutrient–phytoplankton–zooplankton (NPZ) model the time variations of observed and unobserved variables. In addition, we estimate the time evolution of two biological parameters, namely, the specific growth rate and specific mortality of phytoplankton. Our study demonstrates that: (i) the series of time-varying estimates of specific growth rate obtained by sequential data assimilation improves the fitting of the NPZ model to the satellite-derived time series: the model trajectories are closer to the observations than those obtained by implementing static values of the parameter; (ii) the estimates of unobserved variables, i.e., nutrient and zooplankton, obtained from an NPZ model by implementation of a pre-defined parameter evolution can be different from those obtained on applying the sequences of parameters estimated by assimilation; and (iii) the maximum estimated specific growth rate of phytoplankton in the study area is more sensitive to the sea-surface temperature than would be predicted by temperature-dependent functions reported previously. The overall results of the study are potentially useful for enhancing our understanding of the biological response of phytoplankton in a changing environment.

Reconstruction and prediction of variations in the open solar magnetic flux and interplanetary conditions

Historic geomagnetic activity observations have been used to reveal centennial variations in the open solar flux and the near-Earth heliospheric conditions (the interplanetary magnetic field and the solar wind speed). The various methods are in very good agreement for the past 135 years when there were sufficient reliable magnetic observatories in operation to eliminate problems due to site-specific errors and calibration drifts. This review underlines the physical principles that allow these reconstructions to be made, as well as the details of the various algorithms employed and the results obtained. Discussion is included of: the importance of the averaging timescale; the key differences between “range” and “interdiurnal variability” geomagnetic data; the need to distinguish source field sector structure from heliospherically-imposed field structure; the importance of ensuring that regressions used are statistically robust; and uncertainty analysis. The reconstructions are exceedingly useful as they provide calibration between the in-situ spacecraft measurements from the past five decades and the millennial records of heliospheric behaviour deduced from measured abundances of cosmogenic radionuclides found in terrestrial reservoirs. Continuity of open solar flux, using sunspot number to quantify the emergence rate, is the basis of a number of models that have been very successful in reproducing the variation derived from geomagnetic activity. These models allow us to extend the reconstructions back to before the development of the magnetometer and to cover the Maunder minimum. Allied to the radionuclide data, the models are revealing much about how the Sun and heliosphere behaved outside of grand solar maxima and are providing a means of predicting how solar activity is likely to evolve now that the recent grand maximum (that had prevailed throughout the space age) has come to an end.

Interaction between allelic variations in vitamin D receptor and retinoid X receptor genes on metabolic traits

BACKGROUND: Low vitamin D status has been shown to be a risk factor for several metabolic traits such as obesity, diabetes and cardiovascular disease. The biological actions of 1, 25-dihydroxyvitamin D, are mediated through the vitamin D receptor (VDR), which heterodimerizes with retinoid X receptor, gamma (RXRG). Hence, we examined the potential interactions between the tagging polymorphisms in the VDR (22 tag SNPs) and RXRG (23 tag SNPs) genes on metabolic outcomes such as body mass index, waist circumference, waist-hip ratio (WHR), high- and low-density lipoprotein (LDL) cholesterols, serum triglycerides, systolic and diastolic blood pressures and glycated haemoglobin in the 1958 British Birth Cohort (1958BC, up to n = 5,231). We used Multifactor- dimensionality reduction (MDR) program as a non-parametric test to examine for potential interactions between the VDR and RXRG gene polymorphisms in the 1958BC. We used the data from Northern Finland Birth Cohort 1966 (NFBC66, up to n = 5,316) and Twins UK (up to n = 3,943) to replicate our initial findings from 1958BC. RESULTS: After Bonferroni correction, the joint-likelihood ratio test suggested interactions on serum triglycerides (4 SNP - SNP pairs), LDL cholesterol (2 SNP - SNP pairs) and WHR (1 SNP - SNP pair) in the 1958BC. MDR permutation model testing analysis showed one two-way and one three-way interaction to be statistically significant on serum triglycerides in the 1958BC. In meta-analysis of results from two replication cohorts (NFBC66 and Twins UK, total n = 8,183), none of the interactions remained after correction for multiple testing (Pinteraction >0.17). CONCLUSIONS: Our results did not provide strong evidence for interactions between allelic variations in VDR and RXRG genes on metabolic outcomes; however, further replication studies on large samples are needed to confirm our findings.

Activities related with electricity consumption in the Spanish residential sector: variations between days of the week, Autonomous Communities and size of towns

Nowadays the electricity consumption in the residential sector attracts policy and research efforts, in order to propose saving strategies and to attain a better balance between production and consumption, by integrating renewable energy production and proposing suitable demand side management methods. To achieve these objectives it is essential to have real information about household electricity demand profiles in dwellings, highly correlated, among other aspects, with the active occupancy of the homes and to the personal activities carried out in homes by their occupants. Due to the limited information related to these aspects, in this paper, behavioral factors of the Spanish household residents, related to the electricity consumption, have been determined and analyzed, based on data from the Spanish Time Use Surveys, differentiating among the Autonomous Communities and the size of municipalities, or the type of days, weekdays or weekends. Activities involving a larger number of houses are those related to Personal Care, Food Preparation and Washing Dishes. The activity of greater realization at homes is Watching TV, which together with Using PC, results in a high energy demand in an aggregate level. Results obtained enable identify prospective targets for load control and for efficiency energy reduction recommendations to residential consumers.

Centennial variations in sunspot number, open solar flux and streamer belt width: 1. correction of the sunspot number record since 1874

We analyse the widely-used international/ Zürich sunspot number record, R, with a view to quantifying a suspected calibration discontinuity around 1945 (which has been termed the “Waldmeier discontinuity” [Svalgaard, 2011]). We compare R against the composite sunspot group data from the Royal Greenwich Observatory (RGO) network and the Solar Optical Observing Network (SOON), using both the number of sunspot groups, N{sub}G{\sub}, and the total area of the sunspots, A{sub}G{\sub}. In addition, we compare R with the recently developed interdiurnal variability geomagnetic indices IDV and IDV(1d). In all four cases, linearity of the relationship with R is not assumed and care is taken to ensure that the relationship of each with R is the same before and after the putative calibration change. It is shown the probability that a correction is not needed is of order 10{sup}−8{\sup} and that R is indeed too low before 1945. The optimum correction to R for values before 1945 is found to be 11.6%, 11.7%, 10.3% and 7.9% using A{sub}G{\sub}, N{sub)G{\sub}, IDV, and IDV(1d), respectively. The optimum value obtained by combining the sunspot group data is 11.6% with an uncertainty range 8.1-14.8% at the 2σ level. The geomagnetic indices provide an independent yet less stringent test but do give values that fall within the 2σ uncertainty band with optimum values are slightly lower than from the sunspot group data. The probability of the correction needed being as large as 20%, as advocated by Svalgaard [2011], is shown to be 1.6 × 10{sup}−5{\sup}.