Fast acrobatic maneuvers enable arboreal spiders to hunt dangerous prey.

Spiders, the most specious taxon of predators, have evolved an astounding range of predatory strategies, including group hunting, specialized silk traps, pheromone-loaded bolas, and aggressive mimicry. Spiders that hunt prey defended with behavioral, mechanical, or chemical means are under additional selection pressure to avoid injury and death. Ants are considered dangerous because they can harm or kill their predators, but some groups of spiders, such as the Theridiidae, have a very high diversification of ant-hunting species and strategies [J. Liu et al., Mol. Phylogenet. Evol. 94, 658-675 (2016)]. Here, we provide detailed behavioral analyses of the highly acrobatic Australian ant-slayer spider, Euryopis umbilicata (Theridiidae), that captures much larger and defended Camponotus ants on vertical tree trunks. The hunting sequence consists of ritualized steps performed within split seconds, resulting in an exceptionally high prey capture success rate.

A Modular Strategy for the Synthesis of Macrocycles and Medium-Sized Rings via Cyclization/Ring Expansion Cascade Reactions.

Macrocycles and medium-sized rings are important in many scientific fields and technologies but are hard to make using current methods, especially on a large scale. Outlined herein is a strategy by which functionalized macrocycles and medium-sized rings can be prepared using cyclization/ring expansion (CRE) cascade reactions, without resorting to high dilution conditions. CRE cascade reactions are designed to operate exclusively via kinetically favorable 5-7-membered ring cyclization steps; this means that the problems typically associated with classical end-to-end macrocyclization reactions are avoided. A modular synthetic approach has been developed to facilitate the simple assembly of the requisite linear precursors, which can then be converted into an extremely broad range of functionalized macrocycles and medium-sized rings using one of nine CRE protocols.

Durga: an R package for effect size estimation and visualization.

Statistical analysis and data visualization are integral parts of science communication. One of the major issues in current data analysis practice is an overdependency on-and misuse of-p-values. Researchers have been advocating for the estimation and reporting of effect sizes for quantitative research to enhance the clarity and effectiveness of data analysis. Reporting effect sizes in scientific publications has until now been mainly limited to numeric tables, even though effect size plotting is a more effective means of communicating results. We have developed the Durga R package for estimating and plotting effect sizes for paired and unpaired group comparisons. Durga allows users to estimate unstandardized and standardized effect sizes and bootstrapped confidence intervals of the effect sizes. The central functionality of Durga is to combine effect size visualizations with traditional plotting methods. Durga is a powerful statistical and data visualization package that is easy to use, providing the flexibility to estimate effect sizes of paired and unpaired data using different statistical methods. Durga provides a plethora of options for plotting effect size, which allows users to plot data in the most informative and aesthetic way. Here, we introduce the package and its various functions. We further describe a workflow for estimating and plotting effect sizes using example data sets.

Nest excavators' learning walks in the Australian desert ant Melophorus bagoti.

The Australian red honey ant, Melophorus bagoti, stands out as the most thermophilic ant in Australia, engaging in all outdoor activities during the hottest periods of the day during summer months. This species of desert ants often navigates by means of path integration and learning landmark cues around the nest. In our study, we observed the outdoor activities of M. bagoti workers engaged in nest excavation, the maintenance of the nest structure, primarily by taking excess sand out of the nest. Before undertaking nest excavation, the ants conducted a single exploratory walk. Following their initial learning expedition, these ants then engaged in nest excavation activities. Consistent with previous findings on pre-foraging learning walks, after just one learning walk, the desert ants in our study demonstrated the ability to return home from locations 2 m away from the nest, although not from locations 4 m away. These findings indicate that even for activities like dumping excavated sand within a range of 5-10 cm outside the nest, these ants learn and utilize the visual landmark panorama around the nest.

Morphological ant mimics: constrained to imperfection?

Adaptive evolution relies on both heritable variation and selection. Variation is the raw material upon which selection acts, so any mechanism that limits or prevents the generation of heritable variation reduces the power of selection to lead to adaptation. Such limitations are termed evolutionary constraints. While it is widely accepted that constraints play an important role in shaping evolutionary outcomes, their relative importance, as opposed to adaptation, in determining evolutionary outcomes remains a subject of debate. Evolutionary constraints are often evoked as the reason behind the persistence of inaccurate mimicry. Here, we compared the variation and accuracy of body-shape mimicry in ant-mimicking spiders with that of ant-mimicking insects, predicting greater constraints, and hence inaccuracy, in spiders mimicking ants, due to their evolutionary distance from the ant model. We found high inter-species variation in mimetic accuracy, but dorsally, no overall difference in mimetic accuracy between spider and insect mimics, which is inconsistent with a constraint causing inaccurate mimicry. Our study provides empirical evidence suggesting that imperfect mimicry in spiders and insects is predominantly shaped by adaptive processes rather than constraints or chance. Our findings contribute to our understanding of the mechanisms underlying evolutionary diversity and the processes that shape phenotypic outcomes.

Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions.

Two applications of a radical trap based on a homolytic substitution reaction (SH2') are presented for the trapping of short-lived radical intermediates in organic reactions. The first example is a photochemical cyanomethylation catalyzed by a Ru complex. Two intermediate radicals in the radical chain propagation have been trapped and detected using mass spectrometry (MS), along with the starting materials, products and catalyst degradation fragments. Although qualitative, these results helped to elucidate the reaction mechanism. In the second example, the trapping method was applied to study the radical initiation catalyzed by a triethylboronoxygen mixture. In this case, the concentration of trapped radicals was sufficiently high to enable their detection by nuclear magnetic resonance (NMR). Quantitative measurements made it possible to characterize the radical flux in the system under different reaction conditions (including variations of solvent, temperature and concentration) where modelling was complicated by chain reactions and heterogeneous mass transfer.

Mimicry in motion and morphology: do information limitation, trade-offs or compensation relax selection for mimetic accuracy?

Many animals mimic dangerous or undesirable prey as a defence from predators. We would expect predators to reliably avoid animals that closely resemble dangerous prey, yet imperfect mimics are common across a wide taxonomic range. There have been many hypotheses suggested to explain imperfect mimicry, but comparative tests across multiple mimicry systems are needed to determine which are applicable, and which-if any-represent general principles governing imperfect mimicry. We tested four hypotheses on Australian ant mimics and found support for only one of them: the information limitation hypothesis. A predator with incomplete information will be unable to discriminate some poor mimics from their models. We further present a simple model to show that predators are likely to operate with incomplete information because they forage and make decisions while they are learning, so might never learn to properly discriminate poor mimics from their models. We found no evidence that one accurate mimetic trait can compensate for, or constrain, another, or that rapid movement reduces selection pressure for good mimicry. We argue that information limitation may be a general principle behind imperfect mimicry of complex traits, while interactions between components of mimicry are unlikely to provide a general explanation for imperfect mimicry.

Photochemical Methods for Peptide Macrocyclisation.

Photochemical reactions have been the subject of renewed interest over the last two decades, leading to the development of many new, diverse and powerful chemical transformations. More recently, these developments have been expanded to enable the photochemical macrocyclisation of peptides and small proteins. These constructs benefit from increased stability, structural rigidity and biological potency over their linear counterparts, providing opportunities for improved therapeutic agents. In this review, an overview of both the established and emerging methods for photochemical peptide macrocyclisation is presented, highlighting both the limitations and opportunities for further innovation in the field.

Light- and Manganese-Initiated Borylation of Aryl Diazonium Salts: Mechanistic Insight on the Ultrafast Time-Scale Revealed by Time-Resolved Spectroscopic Analysis.

Manganese-mediated borylation of aryl/heteroaryl diazonium salts emerges as a general and versatile synthetic methodology for the synthesis of the corresponding boronate esters. The reaction proved an ideal testing ground for delineating the Mn species responsible for the photochemical reaction processes, that is, involving either Mn radical or Mn cationic species, which is dependent on the presence of a suitably strong oxidant. Our findings are important for a plethora of processes employing Mn-containing carbonyl species as initiators and/or catalysts, which have considerable potential in synthetic applications.

Iridium-Catalyzed Enantioselective Intermolecular Indole C2-Allylation.

The enantioselective intermolecular C2-allylation of 3-substituted indoles is reported for the first time. This directing group-free approach relies on a chiral Ir-(P, olefin) complex and Mg(ClO4 )2 Lewis acid catalyst system to promote allylic substitution, providing the C2-allylated products in typically high yields (40-99 %) and enantioselectivities (83-99 % ee) with excellent regiocontrol. Experimental studies and DFT calculations suggest that the reaction proceeds via direct C2-allylation, rather than C3-allylation followed by in situ migration. Steric congestion at the indole-C3 position and improved π-π stacking interactions have been identified as major contributors to the C2-selectivity.

Compulsive internet use and the development of self-esteem and hope: A four-year longitudinal study.

OBJECTIVE: Compulsive internet use (CIU) has been linked to decrements in mental health and well-being. However, relatively little is known about how CIU relates to evaluations of the self, and in particular, whether CIU is antecedent to or is a consequence of negative evaluations of one's social worth (self-esteem) and general efficacy (hope). To examine this, we explored the longitudinal relations between CIU and the development of self-esteem and hope among adolescents over a four-year period. METHOD: Two thousand eight hundred and nine adolescents completed measures yearly from Grade 8 (MAge = 13.7) to Grade 11. Autoregressive cross-lagged structural equation models were used to test whether CIU influenced or was influenced by self-esteem and hope. RESULTS: We found consistent support for a CIU-as-antecedent model. CIU preceded reductions in trait hope, and small reductions in self-esteem. In contrast, we did not find evidence for a CIU-as-consequence model: low self-esteem and hope did not predict increases in CIU over time. CONCLUSIONS: Our findings suggest that CIU has negative consequences for young people's feelings of goal-efficacy, and that interventions that address the compulsive use of the internet are likely to strengthen hope and self-esteem among young people.

Enantioselective Halolactonization Reactions using BINOL-Derived Bifunctional Catalysts: Methodology, Diversification, and Applications.

A general protocol is described for inducing enantioselective halolactonizations of unsaturated carboxylic acids using novel bifunctional organic catalysts derived from a chiral binaphthalene scaffold. Bromo- and iodolactonization reactions of diversely substituted, unsaturated carboxylic acids proceed with high degrees of enantioselectivity, regioselectivity, and diastereoselectivity. Notably, these BINOL-derived catalysts are the first to induce the bromo- and iodolactonizations of 5-alkyl-4( Z)-olefinic acids via 5- exo mode cyclizations to give lactones in which new carbon-halogen bonds are created at a stereogenic center with high diastereo- and enantioselectivities. Iodolactonizations of 6-substituted-5( Z)-olefinic acids also occur via 6- exo cyclizations to provide δ-lactones with excellent enantioselectivities. Several notable applications of this halolactonization methodology were developed for desymmetrization, kinetic resolution, and epoxidation of Z-alkenes. The utility of these reactions is demonstrated by their application to a synthesis of precursors of the F-ring subunit of kibdelone C and to the shortest catalytic, enantioselective synthesis of (+)-disparlure reported to date.

Moving like a model: mimicry of hymenopteran flight trajectories by clearwing moths of Southeast Asian rainforests.

Clearwing moths are known for their physical resemblance to hymenopterans, but the extent of their behavioural mimicry is unknown. We describe zigzag flights of sesiid bee mimics that are nearly indistinguishable from those of sympatric bees, whereas sesiid wasp mimics display faster, straighter flights more akin to those of wasps. In particular, the flight of the sesiids Heterosphecia pahangensis, Aschistophleps argentifasciata and Pyrophleps cruentata resembles both Tetragonilla collina and T. atripes stingless bees and, to a lesser extent, dwarf honeybees Apis andreniformis, whereas the sesiid Pyrophleps sp. resembles Tachysphex sp. wasps. These findings represent the first experimental evidence for behavioural mimicry in clearwing moths.

A worthy self is a caring self: Examining the developmental relations between self-esteem and self-compassion in adolescents.

OBJECTIVE: Self-compassion has been framed as a healthy alternative to self-esteem, as it is nonevaluative. However, rather than being alternatives, it may be that the two constructs develop in a mutually reinforcing way. The present study tested this possibility among adolescents. METHOD: A large adolescent sample (N = 2,809; 49.8% female) reported levels of trait self-esteem and self-compassion annually for 4 years. Autoregressive cross-lagged structural equation models were used to estimate the reciprocal longitudinal relations between the two constructs. RESULTS: Self-esteem consistently predicted changes in self-compassion across the 4 years of the study, but not vice versa. CONCLUSIONS: Self-esteem appears to be an important antecedent of the development of self-compassion, perhaps because the capacity to extend compassion toward the self depends on one's appraisals of worthiness. These findings add important insights to our theoretical understanding of the development of self-compassion.

Ring-Expansion Reactions in the Synthesis of Macrocycles and Medium-Sized Rings.

Functionalised macrocycles and medium-sized rings have applications in a number of scientific fields, ranging from medicinal chemistry and supramolecular chemistry, to catalysis and nanotechnology. However, their value in these areas can be undermined by a simple, but important limitation: large ring systems are very often difficult to make. Traditional end-to-end cyclisation reactions of long linear precursors are typically unpredictable and impractical processes, mainly due to unfavourable enthalpic and entropic factors. Most published methods to make large rings focus on minimising the damage inflicted by performing the difficult cyclisation step; in contrast, ring-expansion reactions enable it to be avoided altogether. In this Review article, it is highlighted how "growing" rings from existing cyclic systems via ring expansion can expedite the efficient, practical and scalable synthesis of macrocycles and medium-sized rings.

Low-Temperature, Transition-Metal-Free Cross-Dehydrogenative Coupling Protocol for the Synthesis of 3,3-Disubstituted Oxindoles.

A new low-temperature procedure for the synthesis of 3,3-disubstituted 2-oxindoles via cross-dehydrogenative coupling (CDC) is reported. The use of a strong, nonreversible base in these reactions has been found to effect a dramatic drop in reaction temperature (to room temperature) relative to the current state-of-the-art (>100 °C) procedure. When employing iodine as an "oxidant", new evidence suggests that this transformation may occur via a transiently stable iodinated intermediate rather than by direct single-electron oxidation.

Photoredox-catalyzed procedure for carbamoyl radical generation: 3,4-dihydroquinolin-2-one and quinolin-2-one synthesis.

A reductive approach for carbamoyl radical generation from N-hydroxyphthalimido oxamides under photoredox catalysis is outlined. This strategy was applied to the synthesis of 3,4-dihydroquinolin-2-ones via the intermolecular addition/cyclization of carbamoyl radicals with electron deficient olefins in a mild, redox-neutral manner. Under a general set of reaction conditions, diversely substituted 3,4-dihydroquinolin-2-ones, including spirocyclic systems can be prepared. By using chlorine-substituted olefins, aromatic quinolin-2-ones can also be accessed.

Cognitive Defusion Predicts More Approach and Less Avoidance Coping With Stress, Independent of Threat and Self-Efficacy Appraisals.

OBJECTIVE: Recent evidence suggests that the way in which individuals relate to their aversive thoughts predicts behavioral effectiveness more than the content of such thoughts. This article is among the first to explore whether this is true for coping with stressful events. METHOD: Three studies with emerging adults (Study 1, N = 202) and adults (Study 2, N = 201; Study 3, N = 141) tested whether changes in how individuals relate to their stress-related thoughts, measured using the individual-difference construct of cognitive defusion, predicted more approach and less avoidance coping behavior, controlling for stress-related appraisals. RESULTS: We found that cognitive defusion predicted more approach coping (Studies 1 and 3) and less avoidance coping (Studies 2 and 3) following laboratory-induced stress (Study 1), naturally occurring monthly stress (Study 2), and daily stress (Study 3). These effects occurred independently of the effects of threat appraisals (Studies 1-3) and self-efficacy appraisals (Study 3) on coping responses. CONCLUSIONS: Cognitive defusion may be an important individual-difference predictor of coping behavior, adding to established theories of coping such as Lazarus and Folkman's (1987) transactional theory.

Cross-species chimeras reveal BamA POTRA and ß-barrel domains must be fine-tuned for efficient OMP insertion.

BAM is a conserved molecular machine, the central component of which is BamA. Orthologues of BamA are found in all Gram-negative bacteria, chloroplasts and mitochondria where it is required for the folding and insertion of ß-barrel containing integral outer membrane proteins (OMPs) into the outer membrane. BamA binds unfolded ß-barrel precursors via the five polypeptide transport-associated (POTRA) domains at its N-terminus. The C-terminus of BamA folds into a ß-barrel domain, which tethers BamA to the outer membrane and is involved in OMP insertion. BamA orthologues are found in all Gram-negative bacteria and appear to function in a species-specific manner. Here we investigate the nature of this species-specificity by examining whether chimeric Escherichia coli BamA fusion proteins, carrying either the ß-barrel or POTRA domains from various BamA orthologues, can functionally replace E. coli BamA. We demonstrate that the ß-barrel domains of many BamA orthologues are functionally interchangeable. We show that defects in the orthologous POTRA domains can be rescued by compensatory mutations within the ß-barrel. These data reveal that the POTRA and barrel domains must be precisely aligned to ensure efficient OMP insertion.

The Families of Non-LTR Transposable Elements within Neritimorpha and Other Gastropoda.

Repeated sequences, especially transposable elements (TEs), are known to be abundant in some members of the important invertebrate class Gastropoda. TEs that do not have long terminal repeated sequences (non-LTR TEs) are frequently the most abundant type but have not been well characterised in any gastropod. Despite this, sequences in draft gastropod genomes are often described as non-LTR TEs, but without identification to family type. This study was conducted to characterise non-LTR TEs in neritimorph snails, using genomic skimming surveys of three species and the recently published draft genome of Theodoxus fluviatilis. Multiple families of non-LTR TEs from the I, Jockey, L1, R2 and RTE superfamilies were found, although there were notably few representatives of the first of these, which is nevertheless abundant in other Gastropoda. Phylogenetic analyses of amino acid sequences of the reverse transcriptase domain from the elements ORF2 regions found considerable interspersion of representatives of the four neritimorph taxa within non-LTR families and sub-families. In contrast, phylogenetic analyses of sequences from the elements' ORF1 region resolved the representatives from individual species as monophyletic. However, using either region, members of the two species of the Neritidae were closely related, suggesting their potential for investigation of phyletic evolution at the family level.