A comparison of scytonemin and its carbon analogue in terms of antioxidant properties through free radical mechanisms and conformational analysis: a DFT investigation

Scytonemin is a UV absorbing sheath pigment synthesized uniquely by cyanobacteria. Its biological features has attracted interest ecologically (in microbial mat systems), medically (for therapeutic activity) and astrobiologically (as a key biomarker). Recently, a carbon analogue of scytonemin, in which two nitrogen atoms are replaced by carbon atoms was synthesized to elucidate the origin of biological activity by comparison with scytonemin. In this work, their structural/conformational aspects and relative antioxidant capacity are compared making use of DFT calculations to provide insight about the similarities and differences between the two. The carbon analogue of scytonemin, isoelectronic with scytonemin, has the same structural skeleton and a similar potential energy surface but the hydrogens on the carbons that replace the nitrogens cause the phenolic rings to rotate out of the plane which is obseved for scytonemin. Thermochemically, the carbon analogue of scytonemin prefers the same radical scavenging mechanism scytonemin does, the HAT mechanism, and has a lower homolytic bond dissociation enthalpy for the OH group than that of scytonemin and other known antioxidants like ascorbic acid. The carbon analogue of scytonemin is suggested to be a novel synthetic antioxidant.     

The Causes and Evolutionary Consequences of Mixed Singing in Two Hybridizing Songbird Species (Luscinia spp.)

Bird song plays an important role in the establishment and maintenance of prezygotic reproductive barriers. When two closely related species come into secondary contact, song convergence caused by acquisition of heterospecific songs into the birds’ repertoires is often observed. The proximate mechanisms responsible for such mixed singing, and its effect on the speciation process, are poorly understood. We used a combination of genetic and bioacoustic analyses to test whether mixed singing observed in the secondary contact zone of two passerine birds, the Thrush Nightingale (Luscinia luscinia) and the Common Nightingale (L. megarhynchos), is caused by introgressive hybridization. We analysed song recordings of both species from allopatric and sympatric populations together with genotype data from one mitochondrial and seven nuclear loci. Semi-automated comparisons of our recordings with an extensive catalogue of Common Nightingale song types confirmed that most of the analysed sympatric Thrush Nightingale males were ‘mixed singers’ that use heterospecific song types in their repertoires. None of these ‘mixed singers’ possessed any alleles introgressed from the Common Nightingale, suggesting that they were not backcross hybrids. We also analysed songs of five individuals with intermediate phenotype, which were identified as F₁ hybrids between the Thrush Nightingale female and the Common Nightingale male by genetic analysis. Songs of three of these hybrids corresponded to the paternal species (Common Nightingale) but the remaining two sung a mixed song. Our results suggest that although hybridization might increase the tendency for learning songs from both parental species, interspecific cultural transmission is the major proximate mechanism explaining the occurrence of mixed singers among the sympatric Thrush Nightingales. We also provide evidence that mixed singing does not substantially increase the rate of interspecific hybridization and discuss the possible adaptive value of this phenomenon in nightingales.     

Virtual Prototyping and Parametric Design of 3D-Printed Tablets Based on the Solution of Inverse Problem

The problem of designing tablet geometry and its internal structure that results into a specified release profile of the drug during dissolution was considered. A solution method based on parametric programming, inspired by CAD (computer-aided design) approaches currently used in other fields of engineering, was proposed and demonstrated. The solution of the forward problem using a parametric series of structural motifs was first carried out in order to generate a library of drug release profiles associated with each structural motif. The inverse problem was then solved in three steps: first, the combination of basic structural motifs whose superposition provides the closest approximation of the required drug release profile was found by a linear combination of pre-calculated release profiles. In the next step, the final tablet design was constructed and its dissolution curve found computationally. Finally, the proposed design was 3D printed and its dissolution profile was confirmed experimentally. The computational method was based on the numerical solution of drug diffusion in a boundary layer surrounding the tablet, coupled with erosion of the tablet structure encoded by the phase volume function. The tablets were 3D printed by fused deposition modelling (FDM) from filaments produced by hot-melt extrusion. It was found that the drug release profile could be effectively controlled by modifying the tablet porosity. Custom release profiles were obtained by combining multiple porosity regions in the same tablet. The computational method yielded accurate predictions of the drug release rate for both single- and multi-porosity tablets.     

Ecoinvent 3: assessing water use in LCA and facilitating water footprinting

Purpose

Water footprinting and the assessment of water use in life cycle assessment have become of major interest in sustainability assessments. Various initiatives for combining water resource issues with consumption of products and services have been initiated in the last decade. However, comprehensive databases fulfilling the requirements for addressing these issues have been lacking and are necessary to facilitate efficient and consistent assessments of products and services. To this purpose, ecoinvent focused on integrating appropriate water use data into version 3, since previously water use data has been inconsistently reported and some essential flows were missing. This paper describes the structure of the water use data in ecoinvent, how the data has been compiled and the way it can be used for water footprinting.

Methods

The main changes required for proper assessment of water use are the addition of environmental and product flows in order to allow a water balance over each process. This is in accordance with the strict paradigm in ecoinvent 3 to focus on mass balances, which requires the inclusion of water contents of all products (also for e.g. waste water flows), as well as emissions of water to soil, air and various water bodies. Water inputs from air (e.g. rainwater harvesting) is introduced but is not yet used by any activity.

Results and discussion

Ecoinvent version 3.1 consistently includes the relevant flows to address water use in life cycle assessment (LCA) and calculate water footprints on the product level for most processes including uncertainty information. Although some problems regarding data quality and spatial resolution remain, this is an important step forward and can limit efforts for detailed data collection to the most sensitive processes in the product system. With the combination of data on water use and emissions to water for each process, concentration and corresponding water classes can also be calculated and assessed with existing impact assessment methods.

Conclusions

This comprehensive collection of water use data on the process level facilitates the proper assessment of water use within an LCA and water footprints beyond agricultural production. Especially in LCA, but also in tools for eco-design and specific water footprint, this data is essential and leads to a cost-efficient way of assessing consumption choices and product design decisions with full transparency. It enhances the effectiveness of investing in data collection by performing sensitivity analyses using ecoinvent data to identify the most relevant flows and processes.

     

Codiversification of gastrointestinal microbiota and phylogeny in passerines is not explained by ecological divergence

Vertebrate gut microbiota (GM) is comprised of a taxonomically diverse consortium of symbiotic and commensal microorganisms that have a pronounced effect on host physiology, immune system function and health status. Despite much research on interactions between hosts and their GM, the factors affecting inter‐ and intraspecific GM variation in wild populations are still poorly known. We analysed data on faecal microbiota composition in 51 passerine species (319 individuals) using Illumina MiSeq sequencing of bacterial 16S rRNA (V3–V4 variable region). Despite pronounced interindividual variation, GM composition exhibited significant differences at the interspecific level, accounting for approximately 20%–30% of total GM variation. We also observed a significant correlation between GM composition divergence and host's phylogenetic divergence, with strength of correlation higher than that of GM vs. ecological or life history traits and geographic variation. The effect of host's phylogeny on GM composition was significant, even after statistical control for these confounding factors. Hence, our data do not support codiversification of GM and passerine phylogeny solely as a by‐product of their ecological divergence. Furthermore, our findings do not support that GM vs. host's phylogeny codiversification is driven primarily through trans‐generational GM transfer as the GM vs. phylogeny correlation does not increase with higher sequence similarity used when delimiting operational taxonomic units. Instead, we hypothesize that the GM vs. phylogeny correlation may arise as a consequence of interspecific divergence of genes that directly or indirectly modulate composition of GM.