Selective P4 activation by an organometallic nickel(I) radical: formation of a dinuclear nickel(II) tetraphosphide and related di- and trichalcogenides

The reaction of the 17e nickel(I) radical [CpNi(IDipp)] (1, IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with P4 results in a nickel tetraphosphide [{CpNi(IDipp)}2(μ-η1:η1-P4)] with a butterfly-P42− ligand; related chalcogenides [{CpNi(IDipp)}2(μ-E2)] (E = S, Se, Te) and [{CpNi(IDipp)}2(μ-E3)] (E = S, Se) are formed with S8, Se∞ and Te∞.

The effect of light exposure on the degradation of latent fingerprints on brass surfaces: the use of silver electroless deposition as a visualization technique

We have studied the degradation of sebaceous fingerprints on brass surfaces using silver electroless deposition (SED) as a visualization technique. We have stored fingerprints on brass squares either (i) in a locked dark cupboard or (ii) in glass-filtered natural daylight for periods of 3 h, 24 h, 1 week, 3 weeks, and 6 weeks. We find that fingerprints on brass surfaces degrade much more rapidly when kept in the light than they do under dark conditions with a much higher proportion of high-quality prints found after 3 or 6 weeks of aging when stored in the dark. This process is more marked than for similar fingerprints on black PVC surfaces. Identifiable prints can be achieved on brass surfaces using both SED and cyanoacrylate fuming (CFM). SED is quick and straightforward to perform. CFM is more time-consuming but is versatile and can be applied to a wider range of metal surfaces than SED, for example brass surfaces which have been coated by a lacquer.

Bond-selective energy redistribution in the chemisorption of CH3D and CD3H on Pt{1 1 0}-(1 2): a first-principles molecular dynamics study

We have investigated the chemisorption of CH3D and CD3H on Pt{11 0}-(1 2) by performing first-principles molecular dynamics simulations of the recombinative desorption of CH3D (from adsorbed methyl and deuterium) and of CD3H (from adsorbed trideuteromethyl and hydrogen). Vibrational analysis of the symmetry adapted internal coordinates of the desorbing molecules shows that excitation of the single C– D (C–H) bond in the parent molecule is strongly correlated with energy excess in the reaction coordinate. The results of the molecular dynamics simulations are consistent with observed mode- and bond-specific reactivity measurements for chemisorption of methane and its isotopomers on platinum and nickel surfaces.

In vitro colonic metabolism of coffee and chlorogenic acid results in selective changes in human faecal microbiota growth

Coffee is a relatively rich source of chlorogenic acids (CGA), which, like other polyphenols are postulated to exert preventative effects against cardiovascular disease and type-2 diabetes. As a considerable proportion of ingested CGA reaches the large intestine, CGA may be capable of exerting beneficial effects in the large gut. Here we utilise a stirred, anaerobic, pH controlled, batch culture fermentation model of the distal region of the colon in order to investigate the impact of coffee and CGA on the growth of the human faecal microbiota. Incubation of the coffee with the human faecal microbiota led to the rapid metabolism of CGA (4h) and the production of dihydrocaffeic acid and dihydroferulic acid, whilst caffeine remained un-metabolised. The coffee with the highest levels of CGA (p<0.05, relative to the other coffees) induced a significant increase in Bifidobacterium spp. relative to the control at 10 hours post exposure (p<0.05). Similarly, an equivalent quantity of CGA (80.8mg; matched with that in high CGA coffee) induced a significant increase in Bifidobacterium spp. (p<0.05). CGA alone also induced a significant increase in the Clostridium coccoides-Eubacterium rectale group (p<0.05). This selective metabolism and subsequent amplification of specific bacterial populations could be beneficial to host health.

Low complexity equalization of HCM systems with DPFFT demodulation over doubly-selective channels

To mitigate the inter-carrier interference (ICI) of doubly-selective (DS) fading channels, we consider a hybrid carrier modulation (HCM) system employing the discrete partial fast Fourier transform (DPFFT) demodulation and the banded minimum mean square error (MMSE) equalization in this letter. We first provide the discrete form of partial FFT demodulation, then apply the banded MMSE equalization to suppress the residual interference at the receiver. The proposed algorithm has been demonstrated, via numerical simulations, to be its superior over the single carrier modulation (SCM) system and circularly prefixed orthogonal frequency division multiplexing (OFDM) system over a typical DS channel. Moreover, it represents a good trade-off between computational complexity and performance.

nor-Mevaldic acid surrogates as selective antifungal agent leads against Botrytis cinerea. Enantioselective preparation of 4-hydroxy-6-(1-phenylethoxy)tetrahydro-2H-pyran-2-one

Solvent-free desymmetrisation of meso-dialdehyde 1 with chiral 1-phenylethan-1-ol, led to preparation of 4-silyloxy-6-alkyloxytetrahydro-2H-pyran-2-one (+)-3a with a 96:4 d.r. Deprotected lactone (+)-19a and the related racemic lactones 16a-18a present a lactone moiety resembling the natural substrate of HMG-CoA reductase and their antifungal properties have been evaluated against the phytopathogenic fungi Botrytis cinerea and Colletotrichum gloeosporioides. These compounds were selectively active against B. cinerea, while inactive against C. gloeosporioides.

Hydrophilic sulfonated bis-1,2,4-triazine ligands are highly effective reagents for separating actinides(iii) from lanthanides(iii) via selective formation of aqueous actinide complexes

We report the first examples of hydrophilic 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) ligands, and their applications as actinide(III) selective aqueous complexing agents. The combination of a hydrophobic diamide ligand in the organic phase and a hydrophilic tetrasulfonated bis-triazine ligand in the aqueous phase is able to separate Am(III) from Eu(III) by selective Am(III) complex formation across a range of nitric acid concentrations with very high selectivities, and without the use of buffers. In contrast, disulfonated bis-triazine ligands are unable to separate Am(III) from Eu(III) in this system. The greater ability of the tetrasulfonated ligands to retain Am(III) selectively in the aqueous phase than the corresponding disulfonated ligands appears to be due to the higher aqueous solubilities of the complexes of the tetrasulfonated ligands with Am(III). The selectivities for Am(III) complexation observed with hydrophilic tetrasulfonated bis-triazine ligands are in many cases far higher than those found with the polyaminocarboxylate ligands previously used as actinide-selective complexing agents, and are comparable to those found with the parent hydrophobic bis-triazine ligands. Thus we demonstrate a feasible alternative method to separate actinides from lanthanides than the widely studied approach of selective actinide extraction with hydrophobic bis-1,2,4-triazine ligands such as CyMe4-BTBP and CyMe4-BTPhen.

Time is of the essence: a selective review of the fall and rise of brief therapy research

For compelling reasons of equity and the advance of public health, brief psychotherapy has become the dominant format in both practice and research. One consequence of this is the apparent decline of a distinct stream of brief therapy research. However, much of the agenda formerly identified with that research stream is of increasing importance to the field. Time is indeed of the essence in current psychotherapy research. For example, factors conducive to the time efficiency of brief psychodynamic therapy have been described recently. The important question ‘How much therapy is enough?’ has been addressed by studies inspired by the dose-response analysis of Howard and colleagues. The value of ultra-brief interventions has been examined. These issues are considered in a selective review, drawing in particular on the work of the Sheffield/Leeds psychotherapy of depression research group. This research treats the number of treatment sessions as an independent variable, thereby providing a causal analysis of the dose-response relationship over a range from two to 16 sessions, illuminated by a comparative analysis of change processes in treatments of different durations. Its results enable some specification of the extent and nature of incremental benefit derived from additional sessions in the psychotherapy of depression.

Recovering the counterfactual wage distribution with selective return migration

This paper recovers the distribution of wages for Mexican-born workers living in the U.S. if no return migration of Mexican-born workers occurred. Because migrants self-select in the decision to return, the overarching problem addressed by this study is the use of an estimator that also accounts for selection on unobservables. I find that Mexican returnees are middle- to high-wage earners at all levels of educational attainment. Taking into account self-selection in return migration, wages would be approximately 7.7% higher at the median and 4.5% higher at the mean. Owing to positive self-selection, the immigrant-native wage gap would, therefore, partially close if there was no return migration.

Rapid selective separation of americium/curium from simulated nuclear forensic matrices using triazine ligands

In analysis of complex nuclear forensic samples containing lanthanides, actinides and matrix elements, rapid selective extraction of Am/Cm for quantification is challenging, in particular due the difficult separation of Am/Cm from lanthanides. Here we present a separation process for Am/Cm(III) which is achieved using a combination of AG1-X8 chromatography followed by Am/Cm extraction with a triazine ligand. The ligands tested in our process were CyMe4-BTPhen, CyMe4- BTBP, CA-BTP and CA-BTPhen. Our process allows for purification and quantification of Am and Cm (recoveries 80%–100%) and other major actinides in < 2d without the use of multiple columns or thiocyanate. The process is unaffected by high level Ca(II)/Fe(III)/Al(III) (10mg mL−1) and thus requires little pre-treatment of samples.

Selective environmental stress caused by magmatic sulfur emissions from continental flood basalt eruptions

Several biotic crises during the past 300 million years have been linked to episodes of continental flood basalt volcanism, and in particular to the release of massive quantities of magmatic sulphur gas species. Flood basalt provinces were typically formed by numerous individual eruptions, each lasting years to decades. However, the environmental impact of these eruptions may have been limited by the occurrence of quiescent periods that lasted hundreds to thousands of years. Here we use a global aerosol model to quantify the sulphur-induced environmental effects of individual, decade-long flood basalt eruptions representative of the Columbia River Basalt Group, 16.5–14.5 million years ago, and the Deccan Traps, 65 million years ago. For a decade-long eruption of Deccan scale, we calculate a decadal-mean reduction in global surface temperature of 4.5 K, which would recover within 50 years after an eruption ceased unless climate feedbacks were very different in deep-time climates. Acid mists and fogs could have caused immediate damage to vegetation in some regions, but acid-sensitive land and marine ecosystems were well-buffered against volcanic sulphur deposition effects even during century-long eruptions. We conclude that magmatic sulphur from flood basalt eruptions would have caused a biotic crisis only if eruption frequencies and lava discharge rates had been high and sustained for several centuries at a time.

‘Symptomless’ infection by Botrytis cinerea

The study was carried out to clarify the nature of symptomless infection by Botrytis cinerea and to what extent it differs from aggressive necrotic infection in Lactuca sativa (lettuce) and Arabidopsis thaliana. Symptomless plants were produced by dry spore inoculation in plants growing in controlled environmental conditions or in glasshouses. Plating out of surface-disinfected and non-surface-disinfected samples of inoculated, apparently healthy, plants on selective medium revealed that the fungus was spreading from the initial inoculation site to newly developing plant organs both internally and externally. Similar findings were obtained in microscope experiments in which host plants were inoculated with GFP labelled B. cinerea and symptomless spreading was monitored under confocal laser scanning microscope. Spore germination on leaf surface was followed by development of sub-cuticular vesicles and plant cell damage in the infected epidermal cell and a few nearby cells. Sparsely branched long hyphae arose from the vesicles and spread on the leaf surface; spread was mostly on the outer surface of the epidermal layer but occasionally below the cuticle or epidermal cells. In the late symptomless phase, mycelium arising from single vesicles formed several mycelial networks on leaves. Experiments were carried out to compare the extent of gene expression in symptomless and necrotic infections, using RT-qPCR. Expression of selected genes was quantified in tissue samples based on the amount of mRNA of the respective genes found. In both host species, the mRNA concentration of signalling genes bcg1, bmp1 and calcineurin, and the pathogenicity genes bcsod1 and bcpg1 were similar to or slightly greater in symptomless samples than in necrotic samples. The mRNA of the signalling gene bac and pathogenicity genes bcbot1 and bcnep1, were not detected or detected in lower abundance than in necrosis. In lettuce, the leaves developing distant from the site of inoculation showed similar results to A. thaliana, but in healthy leaves close to the site of inoculation mRNA concentrations of bac and bcnep1 were similar to necrotic samples. Thus, in both host species, the fungus grew along with the plant and moved to newly growing plant parts without producing symptoms; during this growth some pathogenicity genes were less expressed than in necrotic infection.

Effects of selective logging on tropical forest tree growth

We combined measurements of tree growth and carbon dioxide exchange to investigate the effects of selective logging on the Aboveground Live Biomass (AGLB) of a tropical rain forest in the Amazon. Most of the measurements began at least 10 months before logging and continued at least 36 months after logging. The logging removed similar to 15% of the trees with Diameter at Breast Height (DBH) greater than 35 cm, which resulted in an instantaneous 10% reduction in AGLB. Both wood production and mortality increased following logging, while Gross Primary Production (GPP) was unchanged. The ratio of wood production to GPP (the wood Carbon Use Efficiency or wood CUE) more than doubled following logging. Small trees (10 cm < DBH < 35 cm) accounted for most of the enhanced wood production. Medium trees (35 cm < DBH < 55 cm) that were within 30 m of canopy gaps created by the logging also showed increased growth. The patterns of enhanced growth are most consistent with logging-induced increases in light availability. The AGLB continued to decline over the study, as mortality outpaced wood production. Wood CUE and mortality remained elevated throughout the 3 years of postlogging measurements. The future trajectory of AGLB and the forest`s carbon balance are uncertain, and will depend on how long it takes for heterotrophic respiration, mortality, and CUE to return to prelogging levels.

Selective preying of the sphecid wasp Trachypus boharti on the meliponine bee Scaptotrigona postica: potential involvement of caste-specific cuticular hydrocarbons

The specialist digger wasp Trachypus boharti Rubio-Espina preys exclusively on males of the stingless bee Scaptotrigona postica Latreille 1807, although the hunting attacks involve both male and worker bees of S. postica and members of its own species. To understand the mechanism of prey selection, the cuticular hydrocarbon patterns of workers and males of S. postica are analyzed in detail, and the mandibular secretion of males is examined. The cuticular profiles of males and workers are distinctively different. The major group of cuticular compounds, heptacosene isomers, is twice as abundant in workers as in males. There is no clear distinction between worker and male mandibular secretions. Such a distinct and straightforward caste-specific difference in cuticular hydrocarbons could function as a recognition cue by which T. boharti distinguishes between workers and males of S. postica.