Aza-cibalackrot: turning on singlet fission through crystal engineering

Singlet fission is a photophysical process that provides a pathway for more efficient harvesting of solar energy in photovoltaic devices. The design of singlet fission candidates is non-trivial and requires careful optimization of two key criteria: (1) correct energetic alignment and (2) appropriate intermolecular coupling. Meanwhile, this optimization must not come at the cost of molecular stability or feasibility for device applications. Cibalackrot is a historic and stable organic dye which, although it has been suggested to have ideal energetics, does not undergo singlet fission due to large interchromophore distances, as suggested by single crystal analysis. Thus, while the energetic alignment is satisfactory, the molecule does not have the desired intermolecular coupling. Herein, we improve this characteristic through molecular engineering with the first synthesis of an aza-cibalackrot and show, using ultrafast transient spectroscopy, that singlet fission is successfully "turned on.

Effects of solute Nb atoms and Nb precipitates on isothermal transformation kinetics from austenite to ferrite

Nb is a very important micro-alloying element in low-carbon steels, for grain size refinement and precipitation strengthening, and even a low content of Nb can result in a significant effect on phase transformation kinetics from austenite to ferrite. Solute Nb atoms and Nb precipitates may have different effects on transformation behaviors, and these effects have not yet been fully characterized. This paper examines in detail the effects of solute Nb atoms and Nb precipitates on isothermal transformation kinetics from austenite to ferrite. The mechanisms of the effects have been analyzed using various microscopy techniques. Many solute Nb atoms were found to be segregated at the austenite/ferrite interface and apply a solute drag effect. It has been found that solute Nb atoms have a retardation effect on ferrite nucleation rate and ferrite grain growth rate. The particle pinning effect caused by Nb precipitates is much weaker than the solute drag effect

Comparison of the euryarchaeal microbial community in guts and food-soil of the soil-feeding termite Cubitermes fungifaber across different soil types

Termites are an important component of tropical soil communities and have a significant affect on the structure and nutrient content of soil. Digestion in termites is related to gut structure, gut physico-chemical conditions and gut symbiotic microbiota. Here we describe the use of 16S rRNA gene sequencing and Terminal-restriction Fragment Length Polymorphism (T-RFLP) analysis to examine methanogenic Archaea (MA) in the guts and food-soil of the soil-feeder Cubitermes fungifaber Sjostedt across a range of soil types. If they are strictly vertically inherited, then MA in guts should be the same in all individuals even if the soils differ across sites. In contrast, gut MA should reflect what is present in soil if populations are merely a reflection of what is ingested as the insects forage. We show clear differences between the euryarchaeal communities in termite guts and in food-soils from five different sites. Analysis of 16S rRNA gene clones indicated little overlap between the gut and soil communities. Gut clones were related to a termite-derived Methanomicrobiales cluster, to Methanobrevibacter and, surprisingly, to the haloalkaliphile Natronococcus. Soil clones clustered with Methanosarcina, Methanomicrococcus or Rice Cluster I. T-RFLP analysis indicated that the archaeal communities in the soil samples differed from site to site, whereas those in termite guts were similar between sites. There was some overlap between the gut and soil communities but these may represent transient populations in either guts or soil. Our data does not support the hypothesis that termite gut MA are derived from their food soil but also does not support a purely vertical transmission of gut microflora

Detection and enumeration of sulphate-reducing bacteria in estuarine sediments by competitive PCR

The distribution of sulphate-reducing bacteria (SRB) in the sediments of the Colne River estuary, Essex, UK covering different saline concentrations of sediment porewater was investigated by the use of quantitative competitive PCR. Here, we show that a new PCR primer set and a new quantitative method using PCR are useful tools for the detection and the enumeration of SRB in natural environments. A PCR primer set selective for the dissimilatory sulphite reductase gene (dsr) of SRB was designed. PCR amplification using the single set of dsr-specific primers resulted in PCR products of the expected size from all 27 SRB strains tested, including Gram-negative and positive species. Sixty clones derived from sediment DNA using the primers were sequenced and all were closely related with the predicted dsr of SRB. These results indicate that PCR using the newly designed primer set are useful for the selective detection of SRB from a natural sample. This primer set was used to estimate cell numbers by dsr selective competitive PCR using a competitor, which was about 20% shorter than the targeted region of dsr. This procedure was applied to sediment samples from the River Colne estuary, Essex, UK together with simultaneous measurement of in situ rates of sulphate reduction. High densities of SRB ranging from 0.2 - 5.7 × 108 cells ml-1 wet sediment were estimated by the competitive PCR assuming that all SRB have a single copy of dsr. Using these estimates cell specific sulphate reduction rates of 10-17 to 10-15 mol of SO42- cell-1 day-1 were calculated, which is within the range of, or lower than, those previously reported for pure cultures of SRB. Our results show that the newly developed competitive PCR technique targeted to dsr is a powerful tool for rapid and reproducible estimation of SRB numbers in situ and is superior to the use of culture-dependent techniques

Estimates of sulphate reduction rates in Lake Vanda, Antarctica support the proposed recent history of the lake

Lake Vanda, a perennially ice-covered Antarctic lake has a highly stratified structure with a pronounced density gradient from 45 m and is anoxic from 68 rn down. In order to gain a greater understanding of the carbon cycling in the lake we attempted to measure sulphate reduction in the summer of 1994, but rates were below detectable limits of 1.2 x 10(6) mol sulphate yr(-1). Therefore sulphate reduction was estimated by calculating the rate of sulphide diffusion from the anoxic zone. Sulphate reduction rates were estimated to be 17.7 x 10(3) mol sulphate yr(-1), accounting for 30% of planktonic primary production over the whole lake, but over 100% of primary productivity in the deep chlorophyll maximum. Radiocarbon dating of organic matter in the sediment (565 +/- 50 yr BP), suggests that little new organic carbon reaches the sediment from the upper water column. Oxygen diffusion into the anoxic zone could account for only 44% of sulphide reoxidation; therefore, alternative oxidizing potential presumably accounted for the remainder. Sulphate concentration may be controlled by the solubility limit for a mineral phase, perhaps gypsum, as it shows a positive correlation with conductivity, The sulphur species in the anoxic zone are highly enriched in S-34 (sulphate delta S-34 = +42 to +46%, sulphide delta S-34 = +13.9%) which may be explained by either selective removal of sulphide at the oxic/anoxic interface by precipitation of metal sulphides or previous loss of H2S to the atmosphere. While sulphate reduction is an important part of the carbon cycle within the lake, the oligotrophic nature of Lake Vanda means that all microbiological process rates are very low. The data presented suggest a dynamic and complex history for Lake Vanda and are entirely consistent with present theories of the lake's history

Coping with EU Environmental Legislation:Transposition Principles and Practices

A ‘burden reducing’ agenda has spurred an increased interest in how EU environmental legislation is transposed into national legislation—most prominently reflected in the principle of ‘no gold-plating’. Yet, an important question is to what extent transposition principles and practices may ensure a coherent and accessible body of environmental legislation, while at the same time ensuring adequate transposition of EU environmental legislation. This article analyses the existence, or emergence, of transposition principles and practices in three Member States—the United Kingdom, the Netherlands and Denmark. It also examines how EU initiatives may influence these principles and practices. The article concludes that the steering of transposition processes by general transposition principles and objectives alone, and in particular those dominated by a ‘burden reducing’ agenda, has a limited focus on coherence and accessibility with respect to environmental legislation and that such issues deserve more attention in the transposition process

Use of 16S rRNA-targeted oligonucleotide probes to investigate function and phylogeny of sulphate-reducing bacteria and methanogenic archaea in a UK estuary

Sulphate-reducing bacteria (SRB) and methanogenic archaea (MA) are important anaerobic terminal oxidisers of organic matter. However, we have little knowledge about the distribution and types of SRB and MA in the environment or the functional role they play in situ. Here we have utilised sediment slurry microcosms amended with ecologically significant substrates, including acetate and hydrogen, and specific functional inhibitors, to identify the important SRB and MA groups in two contrasting sites on a UK estuary. Substrate and inhibitor additions had significant effects on methane production and on acetate and sulphate consumption in the slurries. By using specific 16S-targeted oligonucleotide probes we were able to link specific SRB and MA groups to the use of the added substrates. Acetate consumption in the freshwater-dominated sediments was mediated by Methanosarcinales under low-sulphate conditions and Desulfobacter under the high-sulphate conditions that simulated a tidal incursion. In the marine-dominated sediments, acetate consumption was linked to Desulfobacter. Addition of trimethylamine, a non-competitive substrate for methanogenesis, led to a large increase in Methanosarcinales signal in marine slurries. Desulfobulbus was linked to non-sulphate-dependent H-2 consumption in the freshwater sediments. The addition of sulphate to freshwater sediments inhibited methane production and reduced signal from probes targeted to Methanosarcinales and Methanomicrobiales, while the addition of molybdate to marine sediments inhibited Desulfobulbus and Desulfobacterium. These data complement our understanding of the ecophysiology of the organisms detected and make a firm connection between the capabilities of species, as observed in the laboratory, to their roles in the environment. (C) 2003 Federation of European Microbiological Societies. Published by Elsevier Science B.V. All rights reserved