New insights into the mechanisms of carbon dioxide mineralization by portlandite

Portlandite (Ca(OH)₂; also known as calcium hydroxide or hydrated lime), an archetypal alkaline solid, interacts with carbon dioxide (CO₂) via a classic acid–base “carbonation” reaction to produce a salt (calcium carbonate: CaCO₃) that functions as a low-carbon cementation agent, and water. Herein, we revisit the effects of reaction temperature, relative humidity (RH), and CO₂ concentration on the carbonation of portlandite in the form of finely divided particulates and compacted monoliths. Special focus is paid to uncover the influences of the moisture state (i.e., the presence of adsorbed and/or liquid water), moisture content and the surface area-to-volume ratio (s_a/v, mm⁻¹) of reactants on the extent of carbonation. In general, increasing RH more significantly impacts the rate and thermodynamics of carbonation reactions, leading to high(er) conversion regardless of prior exposure history. This mitigated the effects (if any) of allegedly denser, less porous carbonate surface layers formed at lower RH. In monolithic compacts, microstructural (i.e., mass-transfer) constraints particularly hindered the progress of carbonation due to pore blocking by liquid water in compacts with limited surface area to volume ratios. These mechanistic insights into portlandite's carbonation inform processing routes for the production of cementation agents that seek to utilize CO₂ borne in dilute (≤30 mol%) post-combustion flue gas streams.     

Dreissenid veliger dynamics along a nearshore to offshore transect in Lake Michigan

Dreissenid mussel veligers compose a substantial component of pelagic biomass in the Great Lakes, yet their dynamics are poorly understood. To evaluate seasonal, spatial, and inter-annual variation in veliger density, we used a 64-μm mesh plankton net (2008, 2013–2016) and a 153-μm mesh plankton net (2007–2016) to collect dreissenid veligers at nearshore (15–25?m depth), transitional (45?m) and offshore (93–110?m) sites in southeast Lake Michigan during March–December. We also evaluated trends in density of recently settled mussels relative to veliger abundance and the density of the standing stock of adult mussels. Veliger density peaked during both summer and fall at all sites, but peak densities in summer were generally higher nearshore, whereas peak densities in the fall were generally higher offshore. The density of veligers in the 153-μm net was overall 28% of that in the 64-μm net, but there was high variability in this comparison among months. Smaller veligers were much more abundant in the 64-μm net, but there was little difference in the size distribution and abundance between nets for the 210–300?μm size classes. Thus, the 153-μm net could still be a useful tool for assessing density trends of larger veligers just prior to their settlement. Newly settled mussels (≤2?mm) were most abundant in summer or fall at the nearshore and offshore sites but were nearly absent at the transitional site despite the high density of veligers there. Factors other than veliger density must play an important role in mussel recruitment.     

How to ‘find’ an error minimized genetic code: neutral emergence as an alternative to direct Darwinian selection for evolutionary optimization

Error minimization (EM) of the standard genetic code (SGC) refers to the assignment of amino acids to codons in such a way that the deleterious impact of mutations is reduced. The SGC is nearly optimal for the property of EM, compared to randomly generated codes, and prompts the question of how the property arose. Brute force searching of alternative genetic codes is unlikely to have occurred, given the high number of alternative codes. Therefore, a heuristic search of ‘code space’, the space of alternative codes, would have been necessary. Uncovering the nature of this heuristic search is key to understanding the evolution of the genetic code, and consequently the origin of life. Scenarios that rely on direct selection for the property of EM require codon reassignments to sample code space, but these are problematic mechanistically. Alternatively, it has been shown that EM may have emerged in a neutral fashion as a byproduct of the process of genetic code expansion. In this scenario, similar amino acids are added to similar codons via the gene duplication of tRNAs and aminoacyl-tRNA synthetases. Mimicking this process via simulation indeed produces high levels of EM in the resulting genetic codes. These observations imply that optimization has occurred by an alternative to direct selection, commonly viewed as the only form of evolutionary optimization followed in nature. I propose that the neutral emergence of EM produced by code expansion is a genetic algorithm but unlike direct selection, the local selection criterion (amino acid and codon similarity) is distant from the global fitness function (EM), leading to the emergent optimization of EM. By presenting this counter example I clarify how evolutionary optimization in biological systems is not restricted to direct selection, and emphasize that additional processes may lead to the production of beneficial traits, via ‘non-Darwinian optimization’.

     

The three Rs of river ecosystem resilience: Resources,recruitment, and refugia

Resilience in river ecosystems requires that organisms must persist in the face of highly dynamic hydrological and geomorphological variations. Disturbance events such as floods and droughts are postulated to shape life history traits that support resilience, but river management and conservation would benefit from greater understanding of the emergent effects in communities of river organisms. We unify current knowledge of taxonomic‐, phylogenetic‐, and trait‐based aspects of river communities that might aid the identification and quantification of resilience mechanisms. Temporal variations in river productivity, physical connectivity, and environmental heterogeneity resulting from floods and droughts are highlighted as key characteristics that promote resilience in these dynamic ecosystems. Three community‐wide mechanisms that underlie resilience are (a) partitioning (competition/facilitation) of dynamically varying resources, (b) dispersal, recolonization, and recruitment promoted by connectivity, and (c) functional redundancy in communities promoted by resource heterogeneity and refugia. Along with taxonomic and phylogenetic identity, biological traits related to feeding specialization, dispersal ability, and habitat specialization mediate organism responses to disturbance. Measures of these factors might also enable assessment of the relative contributions of different mechanisms to community resilience. Interactions between abiotic drivers and biotic aspects of resource use, dispersal, and persistence have clear implications for river conservation and management. To support these management needs, we propose a set of taxonomic, phylogenetic, and life‐history trait metrics that might be used to measure resilience mechanisms. By identifying such indicators, our proposed framework can enable targeted management strategies to adapt river ecosystems to global change.     

Rationally Designed Polypharmacology: α-Helix Mimetics as Dual Inhibitors of the Oncoproteins Mcl-1 and HDM2

Protein–protein interactions (PPIs), many of which are dominated by α-helical recognition domains, play key roles in many essential cellular processes, and the dysregulation of these interactions can cause detrimental effects. For instance, aberrant PPIs involving the Bcl-2 protein family can lead to several diseases including cancer, neurodegenerative diseases, and diabetes. Interactions between Bcl-2 pro-life proteins, such as Mcl-1, and pro-death proteins, such as Bim, regulate the intrinsic pathway of apoptosis. p53, a tumor-suppressor protein, also has a pivotal role in apoptosis and is negatively regulated by its E3 ubiquitin ligase HDM2. Both Mcl-1 and HDM2 are upregulated in numerous cancers, and, interestingly, there is crosstalk between both protein pathways. Recently, synergy has been observed between Mcl-1 and HDM2 inhibitors. Towards the development of new anticancer drugs, we herein describe a polypharmacology approach for the dual inhibition of Mcl-1 and HDM2 by employing three densely functionalized isoxazoles, pyrazoles, and thiazoles as mimetics of key α-helical domains of their partner proteins.     

A boronic acid-based fluorescent hydrogel for monosaccharide detection

A boronic acid-based anthracene fluorescent probe was functionalised with an acrylamide unit to incorporate into a hydrogel system for monosaccharide detection. In solution, the fluorescent probe displayed a strong fluorescence turn-on response upon exposure to fructose, and an expected trend in apparent binding constants, as judged by a fluorescence response where D-fructose>D-galactose>D-mannose>D-glucose. The hydrogel incorporating the boronic acid monomer demonstrated the ability to detect monosaccharides by fluorescence with the same overall trend as the monomer in solution with the addition of D-fructose resulting in a 10-fold enhancement (≤0.25 mol/L).     

Modified Galacto- or Fuco-Clusters Exploiting the Siderophore Pathway to Inhibit the LecA- or LecB-Associated Virulence of Pseudomonas aeruginosa

Galacto- and fuco-clusters conjugated with one to three catechol or hydroxamate motifs were synthesised to target LecA and LecB lectins of Pseudomonas aeruginosa (PA) localised in the outer membrane and inside the bacterium. The resulting glycocluster–pseudosiderophore conjugates were evaluated as Trojan horses to cross the outer membrane of PA by iron transport. The data suggest that glycoclusters with catechol moieties are able to hijack the iron transport, whereas those with hydroxamates showed strong nonspecific interactions. Mono- and tricatechol galactoclusters ( G1C and G3C ) were evaluated as inhibitors of infection by PA in comparison with the free galactocluster ( G0 ). All of them exhibited an inhibitory effect between 46 to 75 % at 100 μM, with a higher potency than G0 . This result shows that LecA localised in the outer membrane of PA is involved in the infection mechanism.     

Chromia Scale Thermally Grown on Pure Chromium Under Controlled <Emphasis Type="Italic">p</Emphasis>(O<Subscript>2</Subscript>) Atmosphere: II—Spallation Investigation Using Photoelectrochemical Techniques at a Microscale

Pure chromium oxidized at 900 °C at low oxygen partial pressure (10^?12 atm) gives duplex Cr₂O₃ scale with an internal part made of equiaxed grains and exhibiting an n-type conduction, and an external part made of columnar grains and exhibiting a p-type conduction. Spalled regions occurring during cooling have been studied with photoelectrochemical techniques at a microscale. New information in the form of a specific image (structural quality image) could be obtained and revealed a level of structural defect density in the internal chromia subscale higher than that measured in the non-spalled region. The results complement the spallation scenario proposed in part I of this work.