Unlocking the catalytic precision of ligand-controlled enzymatic halogenation.

A single-component flavin-dependent halogenase, AetF, has emerged as an attractive biocatalyst for catalyzing halogenation. However, its flavin chemistry remains unexplored and cannot be predicted due to its uniqueness in sequence and structure compared to other flavin-dependent monooxygenases. Here, we investigated the flavin reactions of AetF using transient kinetics.

Correction: Using machine learning to understand age and gender classification based on infant temperament.

[This corrects the article DOI: 10.1371/journal.pone.

Shields against pollution: phytoremediation and impact of particulate matter on trees at Wigry National Park, Poland.

This study examines the impact of airborne particulate matter (PM) and associated trace elements (TEs) on deciduous and coniferous trees at the edge of Wigry National Park in northeast Poland, focusing on pollution levels and the potential for phytoremediation. Researchers measured PM concentrations in the air and on the leaves of , , and , along with photosynthetic indicators (Fv/Fm ratio and performance index). The study found significant differences in pollution intensity across areas with varying levels of human activity.

"What does this mean for our future?" uncertainty management in mothers' narratives about the diagnosis and birth of their child with Down syndrome.

Pregnancy and childbirth are uncertain experiences that become even more so when parents receive an unexpected medical diagnosis for their child. In the present study, we document sources of uncertainty and the tools used to manage uncertainty in 44 mothers' narratives about the birth and diagnosis of their child with Down syndrome (DS); we also explore variability in the sources of uncertainty and uncertainty management tools as a function of whether mothers received a prenatal or postnatal diagnosis of DS for their child. Across our sample, thematic analysis revealed four sources of uncertainty in mothers' narratives: navigating dissonance between parents and providers during diagnosis, managing disclosure of the diagnosis to others, anticipating child-centered challenges and adjusting developmental expectations, and anticipating family-centered challenges and adjusting familial expectations.

A single diiron enzyme catalyses the oxidative rearrangement of tryptophan to indole nitrile.

Nitriles are uncommon in nature and are typically constructed from oximes through the oxidative decarboxylation of amino acid substrates or from the derivatization of carboxylic acids. Here we report a third nitrile biosynthesis strategy featuring the cyanobacterial nitrile synthase AetD. During the biosynthesis of the eagle-killing neurotoxin, aetokthonotoxin, AetD transforms the 2-aminopropionate portion of 5,7-dibromo-L-tryptophan to a nitrile.

Autobiographical memory phenomenology in transgender and cisgender individuals.

Transgender individuals face challenges to identity as they transition from their sex assigned at birth to their affirmed gender. Memories may support a sense of self through the recall of events with more phenomenological detail than others, making them feel closer to the current self. Autobiographical memories of 90 transgender and 90 cisgender adults were compared on self-reported memory phenomenology.

Mothers' reflections on the diagnosis and birth of their child with Down syndrome: Variability based on the timing of the diagnosis.

Previous research has examined parents' reflections on their child's Down syndrome diagnosis based on whether the diagnosis was provided prenatally or after birth, revealing few significant differences; by comparison, few studies have examined parents' reflections on the birth of the child in relation to the timing of the diagnosis. This study was conducted to examine whether mothers differentially reported on and rated the diagnosis, birth, and most recent birthday of their child with DS based on when the diagnosis was provided. Forty-four American mothers of children with DS discussed the birth of their child, when they learned of their child's DS diagnosis, and their child's most recent birthday with a researcher.

Insomnia and behaviorally induced sleep syndrome in undergraduates tested during the COVID-19 pandemic: associations with health, stress, and GPA.

Study Objectives: This study was conducted to determine (1) whether the distribution of undergraduates who endorse insomnia or behaviorally induced insufficient sleep syndrome (BIISS) varied during the coronavirus disease 2019 (COVID-19) pandemic relative to normal sleepers and in comparison to values reported pre-pandemic and (2) whether group (insomnia, BIISS, and normal sleepers) was differentially associated with health, stress, and academic achievement mid-pandemic.

Methods: Two hundred ninety-three undergraduates completed online questionnaires assessing demographics, global sleep quality, insomnia severity, health, and perceived stress; cumulative grade point averages (GPAs) were also collected for each participant.

Results: The proportion of participants in each group did not differ from the pre-pandemic values reported in Williams et al (2020).

Enzymatic Halogenation of Terminal Alkynes.

The biosynthetic installation of halogen atoms is largely performed by oxidative halogenases that target a wide array of electron-rich substrates, including aromatic compounds and conjugated systems. Halogenated alkyne-containing molecules are known to occur in Nature; however, halogen atom installation on the terminus of an alkyne has not been demonstrated in enzyme catalysis. Herein, we report the discovery and characterization of an alkynyl halogenase in natural product biosynthesis.

Oxidative rearrangement of tryptophan to indole nitrile by a single diiron enzyme.

Nitriles are uncommon in nature and are typically constructed from oximes via the oxidative decarboxylation of amino acid substrates or from the derivatization of carboxylic acids. Here we report a third strategy of nitrile biosynthesis featuring the cyanobacterial nitrile synthase AetD. During the biosynthesis of the 'eagle-killing' neurotoxin, aetokthonotoxin, AetD converts the alanyl side chain of 5,7-dibromo-L-tryptophan to a nitrile.

Cynipid galls on oak leaves are resilient to leaf vein disruption.

Oaks serve as host plants for numerous insects, including those forming galls. Galls induced on oaks are completely dependent on leaf resources. Many other folivores damage veins of leaves, which may result in cutting galls off from sources of assimilates, nutrients and water.

Mobile samplers of particulate matter - Flying omnivorous insects in detection of industrial contamination.

Flying insects are potential mobile samplers of airborne particulate matter (PM). However, current knowledge on their susceptibility to PM is limited to pollinators. Insects' capacity for particle surface accumulation depends on the lifestyle, structure of the body integuments, and behavioral patterns.

Cultural differences in earliest memory reports by European and Chinese American university students born in the United States.

Grounded by the ecological systems perspectives proposed by Bronfenbrenner (1977, 1979) and Fivush and Merrill (2016), the present study was conducted to examine whether autobiographical memory (AM) and self-construal differed in young adults raised in the same macrosystem, but with unique microsystems. European American (EA) participants were born in the United States to mothers who were born in the United States ( = 61) and Chinese American (CA) participants were born in the United States to mothers who were born in China ( = 47). Participants completed an online study in which they reported on and rated aspects of their earliest memory; they also completed measures of self-construal and acculturation.

Undergraduate Student Stress, Sleep, and Health Before and during the COVID-19 Pandemic.

Before the COVID-19 pandemic, undergraduate students experienced sleep problems and mental health issues that were negatively associated with academic achievement. Studies comparing undergraduate sleep and health pre- to mid-pandemic have yielded mixed results, necessitating additional research on other cohorts and examination of potential moderators. The present study was conducted to examine whether American undergraduate students tested mid-pandemic experienced poorer sleep, health, and academic achievement relative to students tested pre-pandemic, as well as to examine whether poor sleep during the pandemic was preferentially associated with poorer health in women.

Using machine learning to understand age and gender classification based on infant temperament.

Age and gender differences are prominent in the temperament literature, with the former particularly salient in infancy and the latter noted as early as the first year of life. This study represents a meta-analysis utilizing Infant Behavior Questionnaire-Revised (IBQ-R) data collected across multiple laboratories (N = 4438) to overcome limitations of smaller samples in elucidating links among temperament, age, and gender in early childhood. Algorithmic modeling techniques were leveraged to discern the extent to which the 14 IBQ-R subscale scores accurately classified participating children as boys (n = 2,298) and girls (n = 2,093), and into three age groups: youngest (< 24 weeks; n = 1,102), mid-range (24 to 48 weeks; n = 2,557), and oldest (> 48 weeks; n = 779).

Biocatalytic oxidative cross-coupling reactions for biaryl bond formation.

Biaryl compounds, with two connected aromatic rings, are found across medicine, materials science and asymmetric catalysis. The necessity of joining arene building blocks to access these valuable compounds has inspired several approaches for biaryl bond formation and challenged chemists to develop increasingly concise and robust methods for this task. Oxidative coupling of two C-H bonds offers an efficient strategy for the formation of a biaryl C-C bond; however, fundamental challenges remain in controlling the reactivity and selectivity for uniting a given pair of substrates.

From Tryptophan to Toxin: Nature's Convergent Biosynthetic Strategy to Aetokthonotoxin.

Aetokthonotoxin (AETX) is a cyanobacterial neurotoxin that causes vacuolar myelinopathy, a neurological disease that is particularly deadly to bald eagles in the United States. The recently characterized AETX is structurally unique among cyanotoxins and is composed of a pentabrominated biindole nitrile. Herein we report the discovery of an efficient, five-enzyme biosynthetic pathway that the freshwater cyanobacterium uses to convert two molecules of tryptophan to AETX.

Harnessing -Quinone Methides in Natural Product Biosynthesis and Biocatalysis.

The implementation of -quinone methide (-QM) intermediates in complex molecule assembly represents a remarkably efficient strategy designed by Nature and utilized by synthetic chemists. -QMs have been taken advantage of in biomimetic syntheses for decades, yet relatively few examples of QM-generating enzymes in natural product biosynthetic pathways have been reported. The biosynthetic enzymes that have been discovered thus far exhibit tremendous potential for biocatalytic applications, enabling the selective production of desirable compounds that are otherwise intractable or inherently difficult to achieve by traditional synthetic methods.

Design principles for site-selective hydroxylation by a Rieske oxygenase.

Rieske oxygenases exploit the reactivity of iron to perform chemically challenging C-H bond functionalization reactions. Thus far, only a handful of Rieske oxygenases have been structurally characterized and remarkably little information exists regarding how these enzymes use a common architecture and set of metallocenters to facilitate a diverse range of reactions. Herein, we detail how two Rieske oxygenases SxtT and GxtA use different protein regions to influence the site-selectivity of their catalyzed monohydroxylation reactions.

Adaptation of a simple method to determine the total terpenoid content in needles of coniferous trees.

In ecological research, quantitative methods are often used to measure the total content of metabolites groups (i.e., phenols, carbohydrates).

"Not just a hobby, but a lifestyle": Characteristics, preferences and self-perception of individuals with different levels of involvement in birdwatching.

Birdwatching is one of the most sustainable types of nature-based tourism and, at the same time, a form of recreation that is developing very dynamically. Birdwatching is attracting more and more people, not only professionals, but also amateurs from many countries. Birdwatching research is still relatively embryonic, especially when compared to nature tourism or wildlife tourism.

Temperament, sleep quality, and insomnia severity in university students: Examining the mediating and moderating role of sleep hygiene.

University students commonly experience sleep problems which have implications for daily functioning and academic achievement. For this reason, research is needed to identify modifiable individual difference variables that may contribute to better sleep in this population. Temperament and sleep hygiene may be two such factors.

Quitline Programs Tailored for Mental Health: Initial Outcomes and Feasibility.

Introduction: The general efficacy of quitlines has been widely demonstrated, but uncertainty exists regarding how quitlines might best intervene for persons with mental health conditions. A total of 1 in 5 people in the U.S.