Red Fluorescence from Organic Microdots: Leveraging Foldamer-Linked Azobenzene for Enhanced Stability and Intensity in Bioimaging Applications.

Azobenzene, while relevant, has faced constraints in biological system applications due to its suboptimal quantum yield and short-wavelength emission. This study presents a pioneering strategy for fabricating organic microdots by coupling foldamer-linked azobenzene, resulting in robust fluorescence intensity and stability, especially in aggregated states, thereby showing promise for bioimaging applications. Comprehensive experimental and computational examinations elucidate the mechanisms underpinning enhanced photostability and fluorescence efficacy. In vitro and in vivo evaluations disclose that the external layer of cis-azo-foldamer microdots performs a self-sacrificial function during photo-bleaching. Consequently, these red-fluorescent microdots demonstrate extraordinary structural and photochemical stabilities over extended periods. The conjugation of a ß-peptide foldamer to the azobenzene chromophore through a glycine linker instigates a blue-shifted and amplified π*-n transition. Molecular dynamics simulations reveal that the aggregated state of cis-azo-foldamers fortifies the stability of cis isomers, thereby augmenting fluorescence efficiency. This investigation furnishes crucial insights into conceptualizing novel, biologically inspired materials, promising stable and enduring imaging applications, and carries implications for diverse arenas such as medical diagnostics, drug delivery, and sensing technologies.

Conformational Adaptation of ß-Peptide Foldamers for the Formation of Metal-Peptide Frameworks.

Metal-coordinated frameworks derived from small peptidic ligands have received much attention thanks to peptides' vast structural and functional diversity. Various peptides with partial conformational preferences have been used to build metal-peptide frameworks, however, the use of conformationally constrained ß-peptide foldamers has not been explored yet. Herein we report the first metal-coordination-mediated assembly of ß-peptide foldamers with 12-helical folding propensity. The coordination of Ag+ to the terminal pyridyl moieties afforded a set of metal-peptide frameworks with unique entangled topologies. Interestingly, formation of the network structures was accompanied by notable conformational distortions of the foldamer ligands. As the first demonstration of new metal-peptide frameworks built from modular ß-peptide foldamers, we anticipate that this work will be an important benchmark for further structural evolution and mechanistic investigation.

Exposed Rock Reduces Tree Size, but Not Diversity.

Karst made up of limestone is widely considered a "Noah's ark" of biodiversity. Rock and soil substrates comprise two different site types in karst terrain, although both can support dense forests. However, it is unclear whether and how the presence of exposed rock affects forest diversity and tree size. We established a 2.2 ha plot (200 × 110 m) in an old-growth oak forest (> 300 years) in karst terrain in southwestern China. We classified the plot into rock and soil components; we analyzed plant diversity and tree size in each component using species diversity indices (richness, number of individuals, Shannon-Wiener index, and Pielou evenness index), stand spatial structure parameters, diameter at breast height (DBH), tree height (TH), and tree basal area (BA). We also analyzed the distributional patterns of species at the sites using non-metric multidimensional scaling, then assessed the effects of abiotic environmental variables on diversity and tree size using redundancy analysis. Our results indicated that both site types (i.e., rock and soil) had similar overall species diversity; trees and shrubs were largely distributed at random within the study site. Tree size was evenly differentiated in the community, and trees were dominant, particularly on soil. Trees on rock were in a status of medium mixture, whereas shrubs on rock were highly mixed. The opposite trend was observed for trees and shrubs growing on soil. The DBH, TH, and BA were smaller in trees growing on rock than in trees growing on soil. Abiotic environmental variables had varying effects on the diversity and size of trees at the two site types; they only explained 21.76 and 14.30% of total variation, respectively. These results suggest that exposed rock has the effect of reducing tree size, but not diversity, thus highlighting the important role of rock in maintaining diversity; moreover, the results imply that karst microhabitats may mitigate the impacts of topography on tree diversity and growth. Greater attention should be focused on exposed rock in the conservation and management of karst forests and the restoration of degraded forest ecosystems.

Melatonin Regulates Lipid Metabolism in Porcine Cumulus-Oocyte Complexes via the Melatonin Receptor 2.

Previous studies suggest that the inclusion of melatonin (MTn) in in vitro maturation protocols improves the developmental competence of oocytes by scavenging reactive oxygen species (ROS). However, the molecular mechanisms integrating melatonin receptor (MT)-mediated lipid metabolism and redox signaling during in vitro cumulus-oocyte complex (COC) development still remain unclear. Here, we aimed to elucidate the potential role of MTn receptors in lipid metabolic adjustments during in vitro porcine COC development. We observed that MTn-mediated Gsα-cAMP/PKA signaling facilitated lipolysis primarily through the MT2 receptor and subsequently increased fatty acid (FA) release by hydrolyzing intracellular triglycerides (TGs) in cumulus cells. Furthermore, CD36 was a critical FA transporter that transported available FAs from cumulus cells to oocytes and promoted de novo TG synthesis in the latter. In addition, MTn regulated lipogenesis and intracellular lipolysis to maintain lipid homeostasis and limit ROS production, thereby supporting oocyte cytoplasmic maturation and the subsequent embryo development. Taken together, these findings provide insight into the possible mechanism integrating MT2-mediated lipid homeostasis and redox signaling, which limits ROS production during in vitro COC development. Therefore, understanding the dynamics of the interactions between lipid homeostasis and redox signaling driven by MT2 is necessary in order to predict drug targets and the effects of therapeutics used to improve female reproductive health.

Spatial structural characteristics of forests dominated by Pinus tabulaeformis Carr.

The Chinese pine (Pinus tabulaeformis Carr.) is an ecologically and economically important evergreen coniferous tree which dominates warm temperate forests throughout northern China. We established two permanent plots within the Chinese pine forest in the Jiulong Mountains, Beijing, China. To understand the structural characteristics and dynamics of these plots, we analyzed the spatial structural characteristics within nearest-neighbor relationships using the bivariate distributions of the stand spatial structural parameters: uniform angle index, W; mingling index, M; dominance index, U; and crowding index, C. Results revealed that most trees in the forest were randomly distributed. The predominant individuals and randomly arranged trees were in very dense areas and surrounded by the same species. In addition, both plots exhibited a uniform size differentiation pattern. The two plots differed mainly in the level of species mixture and dominance. The majority of reference trees in the pure Chinese pine forest (plot 1) exhibited poor species mingling and low dominance, whereas trees in the mixed Chinese pine forest (plot 2) were evenly distributed in each mingling class and most trees were of intermediate dominance. The study results are useful for optimizing forest management activities in the studied stands, promoting tree growth, regeneration and habitat diversity, and improving forest quality at a fine scale.