Charge transfer and optoelectronic properties in the triarylamine-based donor–π bridge–acceptor dyes for dye-sensitised solar cells

The triarylamine–based donor–π bridge–acceptor dyes (namely, Ds-3, Ds-5 and Ds-6), with the higher conversion efficiency of sunlight to electricity, have been studied with quantum chemistry methods. The geometrical structure, frontier molecular orbital and electronic vertical excitation energies were calculated by using the density functional theory (DFT) and the time-dependent DFT with the Cam-B3LYP and PBE0 functional. From the calculated results, we perform a three-dimensional real-space analysis, which demonstrates that the lowest energy excited state of the triarylamine-based dye is a charge transfer (CT) excited state and electrons shift from triarylamine to cyanoacrylic acid group. The excited-state oxidation potentials and driving force energy are identified as the essential parameters to study the electron injection ability of the excited dyes. The evaluation of photochemical parameter and the visualised study of CT process provide the important information for revealing the relationship between structure and photochemical property of the triarylamine-based dyes.     

Attract and deter: a dual role for pyrrolizidine alkaloids in plant–insect interactions

Pyrrolizidine alkaloids (PAs) are the major defense compounds of plants in the Senecio genus. Here I will review the effects of PAs in Senecio on the preference and performance of specialist and generalist insect herbivores. Specialist herbivores have evolved adaptation to PAs in their host plant. They can use the alkaloids as cue to find their host plant and often they sequester PAs for their own defense against predators. Generalists, on the other hand, can be deterred by PAs. PAs can also affect survival of generalist herbivores. Usually generalist insects avoid feeding on young Senecio leaves, which contain a high concentration of alkaloids. Structurally related PAs can differ in their effects on insect herbivores, some are more toxic than others. The differences in effects of PAs on specialist and generalists could lead to opposing selection on PAs, which may maintain the genetic diversity in PA concentration and composition in Senecio species.     

Endogeic earthworms modify soil phosphorus,plant growth and interactions in a legume–cereal intercrop

Background and aims

Intercropping of legumes and cereals appears as an alternative agricultural practice to decrease the use of chemical fertilizers while maintaining high yields. A better understanding of the biotic and abiotic factors determining interactions between plants in such associations is required. Our study aimed to analyse the effect of earthworms on the legume–cereal interactions with a focus on the modifications induced by earthworms on the forms of soil phosphorus (P).

Methods

In a glasshouse experiment we investigated the effect of an endogeic earthworm (Allolobophora chlorotica) on the plant biomass and on N and P acquisition by durum wheat (Triticum turgidum durum L.) and chickpea (Cicer arietinum L.) either grown alone or intercropped. The modifications of the different organic and inorganic P forms in the bulk soil were measured.

Results

There was no overyielding of the intercrop in the absence of earthworms. Earthworms had a strong influence on biomass and resource allocation between roots and shoots whereas no modification was observed in terms of total biomass production and P acquisition. Earthworms changed the interaction between the intercropped species mainly by reducing the competition for nutrients. Facilitation (positive plant–plant interactions) was only observed for the root biomass and P acquisition in the presence of earthworms. Earthworms decreased the amount of organic P extracted with NaOH (Po NaOH), while they increased the water soluble inorganic P (Pi H₂O) content.

Conclusions

In this experiment, earthworms could be seen as “troubleshooter” in plant–plant interaction as they reduced the competition between the intercropped species. Our study brings new insights into how earthworms affect plant growth and the P cycle.     

Hydrogen-bonding interactions in adrenaline–water complexes: DFT and QTAIM studies of structures, properties, and topologies

ωB97XD/6-311++G(d,p) calculations were carried out to investigate the hydrogen-bonding interactions between adrenaline (Ad) and water. Six Ad-H(2)O complexes possessing various types of hydrogen bonds (H-bonds) were characterized in terms of their geometries, energies, vibrational frequencies, and electron-density topology. Natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) analyses were performed to elucidate the nature of the hydrogen-bonding interactions in these complexes. The intramolecular H-bond between the amino and carboxyl oxygen atom of Ad was retained in most of the complexes, and cooperativity between the intra- and intermolecular H-bonds was present in some of the complexes. H-bonds in which hydroxyls of Ad/water acted as proton donors were stronger than other H-bonds. Both hydrogen-bonding interactions and structural deformation play important roles in the relative stabilities of the complexes. The intramolecular H-bond was broken during the formation of the most stable complex, which indicates that Ad tends to break the intramolecular H-bond and form two new intermolecular H-bonds with the first water molecule.     

Rotifer–crustacean interactions in a pseudokarstic lake: influence of hydrology

Zooplankton abundance was related to hydrological and environmental variables in a hydrologically dynamic lake fed by a pseudokarstic aquifer. The study period (2002–2006) in Lake Tovel covered different hydrological situations with water residence time (WRT) having the lowest values in 2002 and the highest values in 2003. WRT was negatively correlated with silica concentrations and algal biovolume. Furthermore, the biovolume of small algae was highest in spring and summer, while large algae did not show any pattern. In multivariate analysis, high abundance of crustacean species in autumn and winter was positively related to WRT and negatively to algal biovolume, while high abundance of rotifer species in spring and summer was negatively related to WRT and positively to algal biovolume. With the exception of Keratella cochlearis and Gastropus stylifer, rotifers showed a pattern of crustacean avoidance, and three groups were distinguished: (i) Ascomorpha ecaudis and Polyarthra dolichoptera, (ii) Asplanchna priodonta and Synchaeta spp., and (iii) Filinia terminalis and Keratella quadrata. These groups were associated with different food sources and depths. We suggest that WRT influenced the rotifer–crustacean relationship by wash-out effects and competition for food resources. The dynamics of single rotifer species were attributable to specific feeding requirements and adaptations. In summary, WRT determined the platform for abiotic and biotic interactions that influenced population dynamics of crustaceans and rotifers.     

Snail–periphyton interactions in a prairie lacustrine wetland

This study examined the effects of nutrients and macrophytes on snail grazers and periphyton in a prairie wetland food web. Snails (Gyraulus circumstriatus) and periphyton in large enclosures in a lacustrine wetland, Delta Marsh, MB, Canada were subjected to two experimental treatments, nutrient addition (nitrogen, phosphorus) and macrophyte exclusion (using a porous geotextile carpet) during July and August. Snail biomass and periphyton biomass (on both artificial substrata and submerged macrophytes) increased over time in all treatments, representing seasonal growth. Snail biomass was three times higher on macrophytes than on artificial substrata. In response to nutrient addition, snail biomass was significantly elevated over time on macrophytes but not on artificial substrata. Conversely, periphyton biomass was higher on artificial substrata but not on macrophytes in response to nutrient addition. Snail biomass and periphyton biomass on artificial substrata showed no response to macrophyte exclusion. Snail biomass on all substrata was inversely correlated with turbidity, whereas periphyton biomass showed no relationship with turbidity. Timing of nutrient additions to wetlands may influence whether the response occurs primarily in phytoplankton or in periphyton and macrophytes.     

Two μ1,5-dicyanamide bridged 2D and 3D metal complexes formed by covalent bonding and weak interactions

One 2D and one 3D dicyanamide bridged complexes, [Cu(dca)₂(et₂-en)]_n (1) and [Mn(dca)₂(im)₂]_n (2) [dca=dicyanamide, et₂-en=N,N-diethyl-ethylenediamine, im=imidazole], have been synthesized. Both the complexes are 1D by covalent bonding but interchain H-bonding promotes dimensionality. Moreover, π-π interaction among the imidazole ligands also plays an important role to have an interlocked 3D structure for 2. Magnetic study of both the complexes shows weak antiferromagnetic interaction between the metal centers. The magnetic data have been fitted with appropriate equations yielding best fit parameters for 1: J=−0.58±0.02 cm⁻¹, g=2.11±0.01 with R=3.2×10⁻⁶ and for 2, J=−0.21 cm⁻¹, g=2.00 and R=5.6×10⁻⁴.     

Plant–pollinator interactions in a Mexican Acacia community

Competition for pollination is thought to be an important factor structuring flowering in many plant communities, particularly among plant taxa with morphologically similar and easily accessible flowers. We examined the potential for heterospecific pollen transfer (HPT) in a community of four Acacia species in a highly seasonal tropical habitat in Mexico. Partitioning of pollen flow among sympatric species appears to be achieved, in part, through segregation of flowering in seasonal time, and interspecific differences in pollinator guilds. However, two coflowering species (Acacia macracantha and Acacia angustissima) shared multiple flower visitors, raising the possibility of HPT. Each of these coflowering species showed high intraspecific daily synchrony in pollen release, but dehisce at different times of day. Pollinators rapidly harvested available pollen from one species before abandoning it to visit the flowers of the second later in the day. The activity of shared pollinators, predominantly bees, is thus structured throughout the day, and potential for HPT reduced. Suggestive evidence in favour of a resource partitioning explanation for this pattern is provided by the fact that A. macracantha showed significantly greater intraspecific synchrony when coflowering with a potential competitor (A. angustissima) than when flowering alone. We discuss our results in light of previous work on coflowering acacia assemblages in Tanzania and Australia. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Tethering,evagination, and vesiculation via cell–cell interactions in microvascular flow

Biomechanics and Modeling in Mechanobiology - Vesiculation is a ubiquitous process undergone by most cell types and serves a variety of vital cell functions; vesiculation from erythrocytes, in...     

Predator–prey interactions and metabolic rates are altered in stable and unstable groups in a social fish

Understanding the determinants and consequences of predation effort, success and prey responses is important since these factors affect the fitness of predators and prey. When predators are also invasive species, the impacts on prey can be particularly far-reaching with ultimate ecosystem-level consequences. However, predators are typically viewed as behaviourally fixed within this interaction and it is unclear how variation in predator social dynamics affects predator–prey interactions. Using the invasive eastern mosquitofish Gambusia holbrooki and a native glass shrimp Paratya australiensis in Australia, we investigated how varying levels of social conflict within predator groups influences predator–prey interactions. By experimentally manipulating group stability of G. holbrooki, we show that rates of social conflict were lower in groups with large size differences, but that routine metabolic rates were higher in groups with large size differences. Predation effort and success did not vary depending on group stability, but in stable groups predation effort by aggressive dominants was greater than subordinates. The anti-predator responses of prey to the stability of predator groups were mixed. While more prey utilized shelters when exposed to stable compared to unstable groups of predators, a greater proportion were sedentary when predator groups were unstable. Overall, this study demonstrates predator group stability is modulated by differences in body size and can influence prey responses. Further, it reveals a hidden metabolic cost of living in stable groups despite reduced overt social conflict. For invasive species management, it is therefore important to consider the behavioural and physiological plasticity of the invasive predators, whose complex social interactions and metabolic demands can modulate patterns of predator–prey interactions.     

Gene–gene and gene–environment interactions in ulcerative colitis

Genome-wide association studies (GWAS) have identified at least 133 ulcerative colitis (UC) associated loci. The role of genetic factors in clinical practice is not clearly defined. The relevance of genetic variants to disease pathogenesis is still uncertain because of not characterized gene–gene and gene–environment interactions. We examined the predictive value of combining the 133 UC risk loci with genetic interactions in an ongoing inflammatory bowel disease (IBD) GWAS. The Wellcome Trust Case–Control Consortium (WTCCC) IBD GWAS was used as a replication cohort. We applied logic regression (LR), a novel adaptive regression methodology, to search for high-order interactions. Exploratory genotype correlations with UC sub-phenotypes [extent of disease, need of surgery, age of onset, extra-intestinal manifestations and primary sclerosing cholangitis (PSC)] were conducted. The combination of 133 UC loci yielded good UC risk predictability [area under the curve (AUC) of 0.86]. A higher cumulative allele score predicted higher UC risk. Through LR, several lines of evidence for genetic interactions were identified and successfully replicated in the WTCCC cohort. The genetic interactions combined with the gene-smoking interaction significantly improved predictability in the model (AUC, from 0.86 to 0.89, P = 3.26E?05). Explained UC variance increased from 37 to 42 % after adding the interaction terms. A within case analysis found suggested genetic association with PSC. Our study demonstrates that the LR methodology allows the identification and replication of high-order genetic interactions in UC GWAS datasets. UC risk can be predicted by a 133 loci and improved by adding gene–gene and gene–environment interactions.     

Plant–microbe interactions and nitrogen dynamics during wetland establishment in a desert stream

In late-successional steady state ecosystems, plants and microbes compete for nutrients and nutrient retention efficiency is expected to decline when inputs exceed biotic demand. In carbon (C)-poor environments typical of early primary succession, nitrogen (N) uptake by C-limited microbes may be limited by inputs of detritus and exudates derived from contemporaneous plant production. If plants are N-limited in these environments, then this differential limitation may lead to positive relationships between N inputs and N retention efficiency. Further, the mechanisms of N removal may vary as a function of inputs if plant-derived C promotes denitrification. These hypotheses were tested using field surveys and greenhouse microcosms simulating the colonization of desert stream channel sediments by herbaceous vegetation. In field surveys of wetland (ciénega) and gravelbed habitat, plant biomass was positively correlated with nitrate (NO₃ ^?) concentration. Manipulation of NO₃ ^? in flow-through microcosms produced positive relationships among NO₃ ^? supply, plant production, and tissue N content, and a negative relationship with root:shoot ratio. These results are consistent with N limitation of herbaceous vegetation in Sycamore Creek and suggest that N availability may influence transitions between and resilience of wetland and gravelbed stable states in desert streams. Increased biomass in high N treatments resulted in elevated rates of denitrification and shifts from co-limitation by C and NO₃ ^? to limitation by NO₃ ^? alone. Overall NO₃ ^? retention efficiency and the relative importance of denitrification increased with increasing N inputs. Thus the coupling of plant growth and microbial processes in low C environments alters the relationship between N inputs and exports due to increased N removal under high input regimes that exceed assimilative demand.     

Monarch–parasite interactions in managed and roadside prairies

Roadsides cover an extensive area within the United States, are actively managed, and have been considered potential areas of habitat for several taxa. For monarch butterflies (Danaus plexippus), roadsides may act as important habitat along their migration route by providing nectar and host plant resources, which is especially important considering the loss and fragmentation of monarch habitat throughout their breeding range. However, the interactions between monarchs and their parasites may be altered in these areas by management regimes. Monarchs are infected by Ophryocystis elektroscirrha (OE), an obligate, spore-forming protist of monarchs and queens, and Lespesia archippivora, a generalist tachinid fly parasitoid. Roadsides could increase parasitism by concentrating monarchs in certain areas or decrease parasitism by modifying habitat (e.g., the roadside management practice of mowing could reduce the availability of OE spores by removing the above ground portion of host plants and generating re-growth), including the distribution and abundance of host plants. In this study, we compared the proportion of infected monarchs between roadside prairies and managed prairies to evaluate the potential of roadside prairies as habitat for monarch butterflies. Our results suggest that the proportion of infected monarchs does not differ between roadside prairies and managed prairies. Thus, roadsides may provide habitat for monarchs that is similar in quality (at least in terms of parasitism rates) to managed prairies. The role of roadsides as habitat for monarchs should be considered when developing roadside management strategies.     

Phytosterols and phytosterolemia: gene–diet interactions

Phytosterol intake is recommended as an adjunctive therapy for hypercholesterolemia, and plant sterols/stanols can reduce cholesterol absorption at the intestinal lumen through the Niemann-Pick C1 Like 1 (NPC1L1) transporter pathway by competitive solubilization in mixed micelles. Phytosterol absorption is of less magnitude than cholesterol and is preferably secreted in the intestinal lumen by ABCG5/G8 transporters. Therefore, plasma levels of plant sterols/stanols are negligible compared with cholesterol, under an ordinary diet. The mechanisms of cholesterol and plant sterols absorption and the whole-body pool of sterols are discussed in this chapter. There is controversy about treatment with statins inducing further increase in plasma non-cholesterol sterols raising concerns about the safety of supplementation of plant sterols to such drugs. In addition, increase in plant sterols has also been reported upon consumption of plant sterol-enriched foods, regardless of other treatments. Rare mutations on ABCG5/G8 transporters affecting cholesterol/non-cholesterol extrusion, causing sitosterolemia with xanthomas and premature atheroslerotic disease are now known, and cholesterol/plant sterols absorption inhibitor, ezetimibe, emerges as the drug that reduces phytosterolemia and promotes xanthoma regression. On the other hand, common polymorphisms affecting the NPC1L1 transporter can interfere with the action of ezetimibe. Gene-diet interactions participate in this intricate network modulating the expression of genetic variants on specific phenotypes and can also affect the individual response to the hypolipidemic treatment. These very interesting aspects promoted a great deal of research in the field.     

Plant–insect interactions: gentians,seed predators and parasitoid wasps

While studying breeding systems and pollination ecology of nine Gentiana species (G. lutea, G. punctata, G. asclepiadea, G. pneumonanthe, G. cruciata, G. pyrenaica, G. verna, G. utriculosa, and G. nivalis) in the Bulgarian mountains, we recorded number of insects that feed on their maturing seeds. In addition, parasitoid wasps in connection to these seed predators were detected. Insects are identified and the impact on the seed set of afore mentioned Gentiana species is estimated. Fruit capsules of Gentiana spp. from different populations in the mountains in Bulgaria were investigated for the presence or absence of damage by larvae during the period of 16 years. The seed destruction varies among the nine investigated Gentiana species. The insects whose larvae damaged the seed/fruit set belonged mainly to Coleoptera and Diptera. The larvae of lycaenid butterflies, Maculinea spp. (Lepidoptera), were recorded only in seeds of G. asclepiadea, G. pneumonanthe and G. cruciata. Parasitoid wasps from the families Ichneumonidae, Braconidae, and Pteromalidae were identified, some of them new for the fauna of Bulgaria.