Redox-active, dinuclear sandwich compounds [Cp*Fe(μ-L)FeCp*] (L = naphthalene and anthracene)

Although there has been much interest in the chemistry of bimetallic transition metal complexes, compounds with naphthalene or anthracene as bridging ligands are still rare. In this article, we describe the synthesis of the homodinuclear iron complexes [Cp*Fe(μ-η4:η4-L)FeCp*] (1: L = C10H8, 2: L = C14H10; Cp* = η5-C5Me5). The complexes were characterized by 1H and 13C{1H} NMR, UV/Vis, and 57Fe Mössbauer spectroscopy, and their molecular structures were determined by X-ray crystallography. Both complexes are diamagnetic as a result of the strong magnetic coupling of the 17e FeI centers mediated by the polyarene bridge. An analysisof the redox behavior of 1 and 2 by cyclic voltammetry andUV/Vis spectroelectrochemistry shows that the complexes can be oxidized reversibly in two well-separated one-electron steps to the monocation [Cp*Fe(μ-L)FeCp*]+ and the dication [Cp*Fe(μ-L)FeCp*]2+. The reduction to the monoanion [Cp*Fe(μ-L)FeCp*]– was also observed.

Two macrocyclic pentaaza compounds containing pyridine evaluated as novel chelating agents in copper(II) and nickel(II) overload

Two pentaaza macrocycles containing pyridine in the backbone, namely 3,6,9,12,18-pentaazabicyclo[12.3.1] octadeca-1(18),14,16-triene ([15]pyN(5)), and 3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),15,17-triene ([16]pyN(5)), were synthesized in good yields. The acid-base behaviour of these compounds was studied by potentiometry at 298.2 K in aqueous solution and ionic strength 0.10 M in KNO3. The protonation sequence of [15]pyN(5) was investigated by H-1 NMR titration that also allowed the determination of protonation constants in D2O. Binding studies of the two ligands with Ca2+, Ni2+, Cu2+, Zn2+, Cd2+, and Pb2+ metal ions were performed under the same experimental conditions. The results showed that all the complexes formed with the 15-membered ligand, particularly those of Cu2+ and especially Ni2+, are thermodynamically more stable than with the larger macrocycle. Cyclic voltammetric data showed that the copper(II) complexes of the two macrocycles exhibited analogous behaviour, with a single quasi-reversible one-electron transfer reduction process assigned to the Cu(II)/Cu(I) couple. The UV-visible-near IR spectroscopic and magnetic moment data of the nickel(II) complexes in solution indicated a tetragonal distorted coordination geometry for the metal centre. X-band EPR spectra of the copper(II) complexes are consistent with distorted square pyramidal geometries. The crystal structure of [Cu([15]pyN(5))](2+) determined by X-ray diffraction showed the copper(II) centre coordinated to all five macrocyclic nitrogen donors in a distorted square pyramidal environment.

Liquid AP-UV-MALDI enables stable ion yields of multiply charged peptide and protein ions for sensitive analysis by mass spectrometry

In biological mass spectrometry (MS), two ionization techniques are predominantly employed for the analysis of larger biomolecules, such as polypeptides. These are nano-electrospray ionization [1, 2] (nanoESI) and matrix-assisted laser desorption/ionization [3, 4] (MALDI). Both techniques are considered to be “soft”, allowing the desorption and ionization of intact molecular analyte species and thus their successful mass-spectrometric analysis. One of the main differences between these two ionization techniques lies in their ability to produce multiply charged ions. MALDI typically generates singly charged peptide ions whereas nanoESI easily provides multiply charged ions, even for peptides as low as 1000 Da in mass. The production of highly charged ions is desirable as this allows the use of mass analyzers, such as ion traps (including orbitraps) and hybrid quadrupole instruments, which typically offer only a limited m/z range (< 2000–4000). It also enables more informative fragmentation spectra using techniques such as collisioninduced dissociation (CID) and electron capture/transfer dissociation (ECD/ETD) in combination with tandem MS (MS/MS). [5, 6] Thus, there is a clear advantage of using ESI in research areas where peptide sequencing, or in general, the structural elucidation of biomolecules by MS/MS is required. Nonetheless, MALDI with its higher tolerance to contaminants and additives, ease-of-operation, potential for highspeed and automated sample preparation and analysis as well as its MS imaging capabilities makes it an ionization technique that can cover bioanalytical areas for which ESI is less suitable. [7, 8] If these strengths could be combined with the analytical power of multiply charged ions, new instrumental configurations and large-scale proteomic analyses based on MALDI MS(/MS) would become feasible.

Altitude acts as an environmental filter on phylogenetic composition, traits and diversity in bee communities.

Knowledge about the phylogeny and ecology of communities along environmental gradients helps to disentangle the role of competition-driven processes and environmental filtering for community assembly. In this study, we evaluated patterns in species richness, phylogenetic structure and life-history traits of bee communities along altitudinal gradients in the Alps, Germany. We found a linear decline in species richness and abundance but increasing phylogenetic clustering in communities with increasing altitude. The proportion of social- and ground-nesting species, as well as mean body size and altitudinal range of bee communities, increased with increasing altitude, whereas the mean geographical distribution decreased. Our results suggest that community assembly at high altitudes is dominated by environmental filtering effects, whereas the relative importance of competition increases at low altitudes. We conclude that inherent phylogenetic and ecological species attributes at high altitudes pose a threat for less competitive alpine specialists with ongoing climate change.

Projections of UV radiation changes in the 21st century: impact of ozone recovery and cloud effects

Monthly averaged surface erythemal solar irradiance (UV-Ery) for local noon from 1960 to 2100 has been derived using radiative transfer calculations and projections of ozone, temperature and cloud change from 14 chemistry climate models (CCM), as part of the CCMVal-2 activity of SPARC. Our calculations show the influence of ozone depletion and recovery on erythemal irradiance. In addition, we investigate UV-Ery changes caused by climate change due to increasing greenhouse gas concentrations. The latter include effects of both stratospheric ozone and cloud changes. The derived estimates provide a global picture of the likely changes in erythemal irradiance during the 21st century. Uncertainties arise from the assumed scenarios, different parameterizations – particularly of cloud effects on UV-Ery – and the spread in the CCM projections. The calculations suggest that relative to 1980, annually mean UV-Ery in the 2090s will be on average 12% lower at high latitudes in both hemispheres, 3% lower at mid latitudes, and marginally higher (1 %) in the tropics. The largest reduction (16 %) is projected for Antarctica in October. Cloud effects are responsible for 2–3% of the reduction in UV-Ery at high latitudes, but they slightly moderate it at mid-latitudes (1 %). The year of return of erythemal irradiance to values of certain milestones (1965 and 1980) depends largely on the return of column ozone to the corresponding levels and is associated with large uncertainties mainly due to the spread of the model projections. The inclusion of cloud effects in the calculations has only a small effect of the return years. At mid and high latitudes, changes in clouds and stratospheric ozone transport by global circulation changes due to greenhouse gases will sustain the erythemal irradiance at levels below those in 1965, despite the removal of ozone depleting substances.

A low-order model investigation of the analysis of gravity waves in the ensemble Kalman filter.

The behavior of the ensemble Kalman filter (EnKF) is examined in the context of a model that exhibits a nonlinear chaotic (slow) vortical mode coupled to a linear (fast) gravity wave of a given amplitude and frequency. It is shown that accurate recovery of both modes is enhanced when covariances between fast and slow normal-mode variables (which reflect the slaving relations inherent in balanced dynamics) are modeled correctly. More ensemble members are needed to recover the fast, linear gravity wave than the slow, vortical motion. Although the EnKF tends to diverge in the analysis of the gravity wave, the filter divergence is stable and does not lead to a great loss of accuracy. Consequently, provided the ensemble is large enough and observations are made that reflect both time scales, the EnKF is able to recover both time scales more accurately than optimal interpolation (OI), which uses a static error covariance matrix. For OI it is also found to be problematic to observe the state at a frequency that is a subharmonic of the gravity wave frequency, a problem that is in part overcome by the EnKF.However, error in themodeled gravity wave parameters can be detrimental to the performance of the EnKF and remove its implied advantages, suggesting that a modified algorithm or a method for accounting for model error is needed.

A Gaussian-mixture ensemble transform filter

We generalize the popular ensemble Kalman filter to an ensemble transform filter, in which the prior distribution can take the form of a Gaussian mixture or a Gaussian kernel density estimator. The design of the filter is based on a continuous formulation of the Bayesian filter analysis step. We call the new filter algorithm the ensemble Gaussian-mixture filter (EGMF). The EGMF is implemented for three simple test problems (Brownian dynamics in one dimension, Langevin dynamics in two dimensions and the three-dimensional Lorenz-63 model). It is demonstrated that the EGMF is capable of tracking systems with non-Gaussian uni- and multimodal ensemble distributions. Copyright © 2011 Royal Meteorological Society

Geographical variation in total and inorganic arsenic content of polished (white) rice

An extensive data set of total arsenic analysis for 901 polished (white) grain samples, originating from 10 countries from 4 continents, was compiled. The samples represented the baseline (i.e., not specifically collected from arsenic contaminated areas), and all were for market sale in major conurbations. Median total arsenic contents of rice varied 7-fold, with Egypt (0.04 mg/kg) and India (0.07 mg/kg) having the lowest arsenic content while the U.S. (0.25 mg/kg) and France (0.28 mg/kg) had the highest content. Global distribution of total arsenic in rice was modeled by weighting each country’s arsenic distribution by that country’s contribution to global production. A subset of 63 samples from Bangladesh, China, India, Italy, and the U.S. was analyzed for arsenic species. The relationship between inorganic arsenic content versus total arsenic content significantly differed among countries, with Bangladesh and India having the steepest slope in linear regression, and the U.S. having the shallowest slope. Using country-specific rice consumption data, daily intake of inorganic arsenic was estimated and the associated internal cancer risk was calculated using the U.S. Environmental Protection Agency (EPA) cancer slope. Median excess internal cancer risks posed by inorganic arsenic ranged 30-fold for the 5 countries examined, being 0.7 per 10,000 for Italians to 22 per 10,000 for Bangladeshis, when a 60 kg person was considered.

Low cost, patterning of human hNT brain cells on parylene-C with UV & IR laser machining

This paper describes the use of 800nm femtosecond infrared (IR) and 248nm nanosecond ultraviolet (UV) laser radiation in performing ablative micromachining of parylene-C on SiO2 substrates for the patterning of human hNT astrocytes. Results are presented that support the validity of using IR laser ablative micromachining for patterning human hNT astrocytes cells while UV laser radiation produces photo-oxidation of the parylene-C and destroys cell patterning. The findings demonstrate how IR laser ablative micromachining of parylene-C on SiO2 substrates can offer a low cost, accessible alternative for rapid prototyping, high yield cell patterning.

Gallium-sulphide supertetrahedral clusters as building blocks of covalent organic-inorganic networks

The synthesis and characterisation of novel covalent organic-inorganic architectures containing organically-functionalised supertetrahedra is described. The structures of these unique materials consist of one-dimensional zigzag chains or of honeycomb-type layers, in which gallium-sulfide supertetrahedral clusters and dipyridyl ligands alternate.

A three-dimensional open-framework indium selenide: [C7H10N][In9Se14]

An open-framework indium selenide, [C7H10N][In9Se14], has been prepared under solvothermal conditions in the presence of 3,5-dimethylpyridine, and characterized by single crystal diffraction, thermogravimetry, elemental analysis, FTIR spectroscopy and UV-Vis diffuse reflectance. The crystal structure of [C7H10N][In9Se14] contains an unusual building unit, in which corner-linked and edge-linked InSe45- tetrahedra coexist. The presence of one-dimensional circular channels, of ca. 6 Å diameter, results in approximately 25% of solvent accessible void space.

Quantification of UV-B flux through time using UV-B-absorbing compounds contained in fossil Pinus sporopollenin

• UV-B radiation currently represents c. 1.5% of incoming solar radiation. However, significant changes are known to have occurred in the amount of incoming radiation both on recent and on geological timescales. Until now it has not been possible to reconstruct a detailed measure of UV-B radiation beyond c. 150 yr ago. • Here, we studied the suitability of fossil Pinus spp. pollen to record variations in UV-B flux through time. In view of the large size of the grain and its long fossil history, we hypothesized that this grain could provide a good proxy for recording past variations in UV-B flux. • Two key objectives were addressed: to determine whether there was, similar to other studied species, a clear relationship between UV-B-absorbing compounds in the sporopollenin of extant pollen and the magnitude of UV-B radiation to which it had been exposed; and to determine whether these compounds could be extracted from a small enough sample size of fossil pollen to make reconstruction of a continuous record through time a realistic prospect. • Preliminary results indicate the excellent potential of this species for providing a quantitative record of UV-B through time. Using this technique, we present the first record of UV-B flux during the last 9500 yr from a site near Bergen, Norway.

Controls on inorganic nitrogen leaching from Finnish catchments assessed using a sensitivity and uncertainty analysis of the INCA-N model

The semi-distributed, dynamic INCA-N model was used to simulate the behaviour of dissolved inorganic nitrogen (DIN) in two Finnish research catchments. Parameter sensitivity and model structural uncertainty were analysed using generalized sensitivity analysis. The Mustajoki catchment is a forested upstream catchment, while the Savijoki catchment represents intensively cultivated lowlands. In general, there were more influential parameters in Savijoki than Mustajoki. Model results were sensitive to N-transformation rates, vegetation dynamics, and soil and river hydrology. Values of the sensitive parameters were based on long-term measurements covering both warm and cold years. The highest measured DIN concentrations fell between minimum and maximum values estimated during the uncertainty analysis. The lowest measured concentrations fell outside these bounds, suggesting that some retention processes may be missing from the current model structure. The lowest concentrations occurred mainly during low flow periods; so effects on total loads were small.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297UV/Vis/NIR and electron paramagnetic resonance (EPR) spectroelectrochemically detectable RuIII species, whereas the reduction proceeds less reversibly and yields predominantly (R-DAB)-ligand-based spin for the 4-methoxyphenyl derivative, measured at low temperature. The results are discussed with respect to metal-to-ligand chargetransfer (MLCT) excited states of conventional (α-diimine)- ruthenium(II) complexes and in view of other (α-diimine)- metal complexes with ambiguous oxidation-state assignments.

The design of UV absorbing systems for horticultural applications

The synthesis and fluorescence behavior of a series of bis(trisilylalkyl)anthracene molecules is described. The photodegradation of these molecules under UV light has been monitored and compared to a commercially available fluorescent optical brightener. There is a relationship between the structure and the rate of photo decay. The materials with more bulky substituents exhibit the greater stability towards UV. For bis(triphenylsilyl)anthracene the photostability appears to be comparable with a commercially available optical brightener, but the molecule may be susceptible to thermal decay.