Origin of electronic absorption spectra of MLCT-excited and one-electron reduced 2,2′-bipyridine and 1,10-phenanthroline complexes

UV–Vis absorption spectra of one-electron reduction products and 3MLCT excited states of [ReICl(CO)3- (N,N)] (N,N = 2,20-bipyridine, bpy; 1,10-phenanthroline, phen) have been measured by low-temperature spectroelectrochemistry and UV–Vis transient absorption spectroscopy, respectively, and assigned by open-shell TD-DFT calculations. The characters of the electronic transitions are visualized and analyzed using electron density redistribution maps. It follows that reduced and excited states can be approximately formulated as [ReICl(CO)3(N,Nÿ)]ÿ and ⁄[ReIICl(CO)3(N,Nÿ)], respectively. UV–Vis spectra of the reduced complexes are dominated by IL transitions, plus weaker MLCT contributions. Excited-state spectra show an intense band in the UV region of 50% IL origin mixed with LMCT (bpy, 373 nm) or MLCT (phen, 307 nm) excitations. Because of the significant IL contribution, this spectral feature is akin to the principal IL band of the anions. In contrast, the excited-state visible spectral pattern arises from predominantly LMCT transitions, any resemblance with the reduced-state visible spectra being coincidental. The Re complexes studied herein are representatives of a broad class of metal a-diimines, for which similar spectroscopic behavior can be expected.

Evidence for the chaotic origin of Northern Annular Mode variability

Exponential spectra are found to characterize variability of the Northern Annular Mode (NAM) for periods less than 36 days. This corresponds to the observed rounding of the autocorrelation function at lags of a few days. The characteristic persistence timescales during winter and summer is found to be ∼5 days for these high frequencies. Beyond periods of 36 days the characteristic decorrelation timescale is ∼20 days during winter and ∼6 days in summer. We conclude that the NAM cannot be described by autoregressive models for high frequencies; the spectra are more consistent with low-order chaos. We also propose that the NAM exhibits regime behaviour, however the nature of this has yet to be identified.

Evolutionary genomics of the Fox genes: origin of gene families and the ancestry of gene clusters

Over the past decade genomic approaches have begun to revolutionise the study of animal diversity. In particular, genome sequencing programmes have spread beyond the traditional model species to encompass an increasing diversity of animals from many different phyla, as well as unicellular eukaryotes that are closely related to the animals. Whole genome sequences allow researchers to establish, with reasonable confidence, the full complement of any particular family of genes in a genome. Comparison of gene complements from appropriate genomes can reveal the evolutionary history of gene families, indicating when both gene diversification and gene loss have occurred. More than that, however, assembled genomes allow the genomic environment in which individual genes are found to be analysed and compared between species. This can reveal how gene diversification occurred. Here, we focus on the Fox genes, drawing from multiple animal genomes to develop an evolutionary framework explaining the timing and mechanism of origin of the diversity of animal Fox genes. Ancient linkages between genes are a prominent feature of the Fox genes, depicting a history of gene clusters, some of which may be relevant to understanding Fox gene function.

Synergistic effects of geographical strain, temperature and larval food on insecticide tolerance in Callosobruchus maculatus (F.)

This study investigated the multifactorial interaction of various environmental factors including 17 geographical strain (Brazil, Cameroon and Yemen strains), temperature, dose and larval food 18 (cowpea and mungbean) on the response of Callosobruchus maculatus adult to insecticide. All 19 the main factors, their two-way interactions and the four-way interaction had significant effects 20 on C. maculatus response to malathion (an organophosphate insecticide). However, the three-21 way interactions were not statistically significant (except strain x food x dose, P = 0.002). The 22 2 Brazil strain was the most responsive to temperature irrespective of the larval food type. The 23 impact of food type differs from one strain to the other, for instance, the food that imparts higher 24 tolerance in a strain might reduce the tolerance in another. Likewise, the hierarchy of tolerance 25 among the cowpea-reared strains (Brazil > Cameroon > Yemen) was totally different from the 26 mungbean-reared strains (Cameroon > Yemen > Brazil). The reasons for these differences were 27 discussed in the light of their impact on C. maculatus management. The management of both C. 28 maculatus and development of resistance could be complex, hence, the states of a variety of 29 environmental factors need to be considered. This is necessary in order to maximize management 30 success of this bruchid especially in tropical/subtropical developing countries.

Variation in the sensitivity of Callosobruchus (Coleoptera: Bruchidae) acetylcholinesterase to the organophosphate insecticide malaoxon: effect of species, geographical strain and food type

BACKGROUND: Bruchid beetles, Callosobruchus species, are serious pests of economically important grain legumes; their activity in stores is often controlled by use of synthetic insecticides. Esterases are known to be involved in insecticide resistance in insects. However, there is dearth of information on esterase activity in the genus Callosobruchus. In this study we investigated the effect of species, geographical strain and food type on the variation of acetylcholinesterase (AChE) activity and its inhibition by malaoxon (malathion metabolite) using an in vitro spectrophotometric method. RESULT: AChE activity varied significantly among species and strains and also among legume type used for rearing them. Generally irrespective of species, strain or food type, the higher the AChE activity of a population, the higher its inhibition by malaoxon. C. chinensis had the highest AChE activity of the species studied and in the presence of malaoxon it had the lowest remaining AChE activity, while C. rhodesianus retained the highest activity. CONCLUSION: A firsthand knowledge of AChE activity in regional Callosobruchus in line with the prevailing food types should be of utmost importance to grain legume breeders, researchers on plant materials for bruchid control and pesticide manufacturer/applicators for a robust integrated management of these bruchids.

Using seasonal hindcasts to understand the origin of the equatorial cold tongue bias in CGCMs and its impact on ENSO

The cold equatorial SST bias in the tropical Pacific that is persistent in many coupled OAGCMs severely impacts the fidelity of the simulated climate and variability in this key region, such as the ENSO phenomenon. The classical bias analysis in these models usually concentrates on multi-decadal to centennial time series needed to obtain statistically robust features. Yet, this strategy cannot fully explain how the models errors were generated in the first place. Here, we use seasonal re-forecasts (hindcasts) to track back the origin of this cold bias. As such hindcasts are initialized close to observations, the transient drift leading to the cold bias can be analyzed to distinguish pre-existing errors from errors responding to initial ones. A time sequence of processes involved in the advent of the final mean state errors can then be proposed. We apply this strategy to the ENSEMBLES-FP6 project multi-model hindcasts of the last decades. Four of the five AOGCMs develop a persistent equatorial cold tongue bias within a few months. The associated systematic errors are first assessed separately for the warm and cold ENSO phases. We find that the models are able to reproduce either El Niño or La Niña close to observations, but not both. ENSO composites then show that the spurious equatorial cooling is maximum for El Niño years for the February and August start dates. For these events and at this time of the year, zonal wind errors in the equatorial Pacific are present from the beginning of the simulation and are hypothesized to be at the origin of the equatorial cold bias, generating too strong upwelling conditions. The systematic underestimation of the mixed layer depth in several models can also amplify the growth of the SST bias. The seminal role of these zonal wind errors is further demonstrated by carrying out ocean-only experiments forced by the AOCGCMs daily 10-meter wind. In a case study, we show that for several models, this forcing is sufficient to reproduce the main SST error patterns seen after 1 month in the AOCGCM hindcasts.

Ethnic differences in beta-cell function, dietary intake and expression of the metabolic syndrome among UK adults of south Asian, black African-Caribbean and white-European origin at high risk of metabolic syndrome

A cross-sectional analysis of ethnic differences in dietary intake, insulin sensitivity and beta-cell function, using the intravenous glucose tolerance test (IVGTT), was conducted on 497 healthy adult participants of the ‘Reading, Imperial, Surrey, Cambridge, and Kings’ (RISCK) study. Insulin sensitivity (Si) was significantly lower in African-Caribbean (AC) and South Asian (SA) participants [IVGTT-Si; AC: 2.13 vs SA: 2.25 vs white-European (WE): 2.84 (×10−4 mL µU min)2, p < 0.001]. AC participants had a higher prevalence of anti-hypertensive therapy (AC: 19.7% vs SA: 7.5%), the most cardioprotective lipid profile [total:high-density lipoprotein (HDL); AC: 3.52 vs SA: 4.08 vs WE: 3.83, p = 0.03] and more pronounced hyperinsulinaemia [IVGTT–acute insulin response (AIR)] [AC: 575 vs SA: 428 vs WE: 344 mL/µU/min)2, p = 0.002], specifically in female participants. Intake of saturated fat and carbohydrate was lower and higher in AC (10.9% and 50.4%) and SA (11.1% and 52.3%), respectively, compared to WE (13.6% and 43.8%, p < 0.001). Insulin resistance in ACs is characterised by ‘normal’ lipid profiles but high rates of hypertension and pronounced hyperinsulinaemia.