Synthesis and optoelectronic properties of benzoquinone-based donor-acceptor compounds.

Herein, we report a mild and efficient palladium-catalyzed C-H functionalization method to synthesize a series of benzoquinone (BQ)-based charge-transfer (CT) derivatives in good yields. The optoelectronic properties of these compounds were explored both theoretically and experimentally and correlations to their structures were identified as a function of the nature and position of the donor group (meta and para) attached to the benzoquinone acceptor. Compound 3, where benzoquinone is para-conjugated to the diphenylamine donor group, exhibited thermally activated delayed fluorescence (TADF) with a biexponential lifetime characterized by a prompt ns component and a delayed component of 353 µs.

Gold(I)-Catalysed Hydroarylation of 1,3-Disubstituted Allenes with Efficient Axial-to-Point Chirality Transfer.

Hydroarylation of enantioenriched 1,3-disubstituted allenes has the potential to proceed with axial-to-point chirality transfer to yield enantioenriched allylated (hetero)aryl compounds. However, the gold-catalysed intermolecular reaction was previously reported to occur with no chirality transfer owing to competing allene racemisation. Herein, we describe the development of the first intermolecular hydroarylations of allenes to proceed with efficient chirality transfer and summarise some of the key criteria for achieving high regio- and stereoselectivity.

Chirality Transfer in Gold(I)-Catalysed Hydroalkoxylation of 1,3-Disubstituted Allenes.

Gold(I)-catalysed intermolecular hydroalkoxylation of enantioenriched 1,3-disubstituted allenes was previously reported to occur with poor chirality transfer due to rapid allene racemisation. The first intermolecular hydroalkoxylation of allenes with efficient chirality transfer is reported here, exploiting conditions that suppress allene racemisation. A full substrate scope study reveals that excellent regio- and stereoselectivities are achieved when a σ-withdrawing substituent is present.

The dynamics of growth cone morphology.

BACKGROUND: Normal brain function depends on the development of appropriate patterns of neural connections. A critical role in guiding axons to their targets during neural development is played by neuronal growth cones. These have a complex and rapidly changing morphology; however, a quantitative understanding of this morphology, its dynamics and how these are related to growth cone movement, is lacking. RESULTS: Here we use eigenshape analysis (principal components analysis in shape space) to uncover the set of five to six basic shape modes that capture the most variance in growth cone form. By analysing how the projections of growth cones onto these principal modes evolve in time, we found that growth cone shape oscillates with a mean period of 30 min. The variability of oscillation periods and strengths between different growth cones was correlated with their forward movement, such that growth cones with strong, fast shape oscillations tended to extend faster. A simple computational model of growth cone shape dynamics based on dynamic microtubule instability was able to reproduce quantitatively both the mean and variance of oscillation periods seen experimentally, suggesting that the principal driver of growth cone shape oscillations may be intrinsic periodicity in cytoskeletal rearrangements. CONCLUSIONS: Intrinsically driven shape oscillations are an important component of growth cone shape dynamics. More generally, eigenshape analysis has the potential to provide new quantitative information about differences in growth cone behaviour in different conditions.

Positive family connections for families of children with a developmental disability: Cluster randomized controlled trial.

Positive Family Connections is a coproduced, positively oriented, family-systems program for families of children with a developmental disability aged 8-13 years. The study was a feasibility cluster randomized-controlled trial which was registered prospectively (International Standard Randomised Controlled Trial Number 14809884). Families (clusters) were randomized 1:1 to take part in Positive Family Connections immediately or to a waitlist condition and were followed up 4 months and 9 months after randomization. Feasibility outcomes included participant and facilitator recruitment rates, retention, intervention adherence, and fidelity. The proposed primary outcome measure was the family APGAR, a measure of family functioning. Quantitative data were analyzed using multilevel modeling. Sixty families (60 primary parental carers and 13 second carers) were randomized. 73.33% of primary parental carers and 71.43% of second carers in the intervention group attended ≥ 4 intervention sessions, and fidelity of delivery was high (M = 94.02% intervention components delivered). Retention for the proposed primary outcome was 97.26% at 4-month follow-up and 98.63% at 9-month follow-up. Intervention condition was not associated with family APGAR scores at 9-month follow-up (estimate = 0.06, 95% CI [-0.49, 0.61], p = .86, Hedges' g = 0.03, 95% CI [-0.43, 0.49]). However, meaningful improvements were observed for other secondary outcomes related to parental well-being and family relationships. A definitive randomized-controlled trial of Positive Family Connections is feasible. Preliminary evaluation of outcomes shows that Positive Family Connections may be beneficial for parental psychological well-being and family relationships. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

Hemp-Based Sustainable Slippery Surfaces: Icephobic and Antithrombotic Properties.

With the passage of the 2018 Farm Bill that removed hemp from the Controlled Substances Act altogether, production of hemp is experiencing a renaissance. Building on this revival and re-emergence of hemp, we designed and fabricated hemp-based sustainable and robust slippery surfaces by coating hemp paper with beeswax and subsequently infusing it with hemp oil. A wide variety of aqueous liquids and beverages easily slide on our hemp-based sustainable slippery surfaces, without leaving a trace. We also fabricated hemp-based sustainable slippery surfaces using different textured metals. Our hemp-based sustainable slippery metal surfaces display good icephobic and antithrombotic properties. With these attributes, we envision that our hemp-based sustainable slippery surfaces will pave the path to more safe, non-toxic, and biodegradable or recyclable slippery surfaces for applications in food packaging, anti-icing or de-icing coatings, and antithrombotic medical devices.

The prevalence and profile of autism in individuals born preterm: a systematic review and meta-analysis.

INTRODUCTION: Preterm birth (<37 weeks) adversely affects development in behavioural, cognitive and mental health domains. Heightened rates of autism are identified in preterm populations, indicating that prematurity may confer an increased likelihood of adverse neurodevelopmental outcomes. The present meta-analysis aims to synthesise existing literature and calculate pooled prevalence estimates for rates of autism characteristics in preterm populations. METHODS: Search terms were generated from inspection of relevant high-impact papers and a recent meta-analysis. Five databases were searched from database creation until December 2020 with PRISMA guidelines followed throughout. RESULTS: 10,900 papers were retrieved, with 52 papers included in the final analyses, further classified by assessment method (screening tools N=30, diagnostic assessment N=29). Pooled prevalence estimates for autism in preterm samples was 20% when using screening tools and 6% when using diagnostic assessments. The odds of an autism diagnosis were 3.3 times higher in individuals born preterm than in the general population. CONCLUSIONS: The pooled prevalence estimate of autism characteristics in individuals born preterm is considerably higher than in the general population. Findings highlight the clinical need to provide further monitoring and support for individuals born preterm.

Sleep disorders in rare genetic syndromes: a meta-analysis of prevalence and profile.

BACKGROUND: Sleep disorders are common in people with intellectual disability (ID) and autism, with growing evidence of diverse sleep profiles across ID associated genetic syndromes. Documenting the prevalence and profile of specific sleep disorders in syndromes will quantify syndrome-driven 'risk', inform prognosis and enhance understanding of aetiology of sleep disorders. METHOD: Following PRISMA guidelines for meta-analysis, we searched Ovid PsycINFO, Ovid MEDLINE, Ovid Embase, Web of Science and PubMed Central with use of syndrome-specific keywords and 60 sleep-related search terms. We screened and extracted papers that reported sleep disorder prevalence data for five or more individuals within a genetic syndrome, and applied quality criteria to produce a quality-effects prevalence model of six types of sleep disorder across nineteen syndromes. Relative risk estimates were calculated for the prevalence of each sleep disorder in each syndrome. RESULTS: Two hundred and seventy three papers were identified, generating 463 prevalence estimates for Angelman, CHARGE, Cornelia de Lange, Down, fragile X, Prader-Willi, Rett, Smith-Magenis and Williams syndromes, mucopolysaccharidoses (MPS disorders), neurofibromatosis and tuberous sclerosis complex. Prevalence estimates were higher in genetic syndromes than published equivalents for typically developing individuals, with few exceptions. Between-syndrome differences for some disorders were evident; sleep-disordered breathing was most prevalent in MPS disorders (72-77%), while excessive daytime sleepiness was highest in Smith-Magenis syndrome (60%). Conversely, insomnia, which was reported at a higher rate than TD estimates in all syndromes except fragile X, was not associated with specific genetic risk. This suggests insomnia could emerge because of the individual's environment or associated developmental delay, rather than any specific genetic syndromes. LIMITATIONS: Due to the broad scope of the meta-analysis, only syndromes previously identified as reporting preliminary sleep research were included. Other syndromes may also experience elevated prevalence rates of specific types of sleep disorder. Only English language papers were included. CONCLUSIONS: Differing prevalence rates between types of sleep disorder suggest differing causal mechanisms, such as cranio-facial morphology in Down and Prader-Willi syndromes and the build-up of mucopolysaccharides in MPS disorders. Priorities for clinical assessment and intervention for sleep disorders are discussed.

Metal-, Photocatalyst-, and Light-Free Direct C-H Acylation and Carbamoylation of Heterocycles.

Direct C-H acylations and carbamoylations of heterocycles can now be readily achieved without requiring any conventional metal, photocatalyst, electrocatalysis, or light activation, thus significantly improving on sustainability, costs, toxicity, waste, and simplicity of the operational procedure. These mild conditions are also suitable for gram-scale reactions and late-stage functionalizations of complex molecules, including pharmaceuticals, N,N-ligands, and light-sensitive molecules.

Diversity and disease: community structure drives parasite transmission and host fitness.

Changes in host diversity and community structure have been linked to disease, but the mechanisms underlying such relationships and their applicability to non-vector-borne disease systems remain conjectural. Here we experimentally investigated how changes in host community structure affected the transmission and pathology of the multi-host parasite Ribeiroia ondatrae, which is a widespread cause of amphibian limb deformities. We exposed larval amphibians to parasites in monospecific or heterospecific communities, and varied host number to differentiate between density- and diversity-mediated effects on transmission. In monospecific communities, exposure to Ribeiroia significantly increased mortality (15%), malformations (40%) and time-to-metamorphosis in toads. However, the presence of tree frogs significantly reduced infection in toads, leading to fewer malformations and higher survival than observed in monospecific communities, providing evidence of parasite-mediated facilitation. Our results suggest that interspecific variation in parasite resistance can inhibit parasite transmission in multi-species communities, reducing infection and pathology in sensitive hosts.

Metal-, Photocatalyst-, and Light-Free, Late-Stage C-H Alkylation of Heteroarenes and 1,4-Quinones Using Carboxylic Acids.

Contrary to the accepted convention, this work shows that Minisci-type C-H alkylation does not require any metal, photocatalyst, light, or prefunctionalization of the readily available and inexpensive carboxylic acids to proceed well under mild conditions. These mild conditions can be utilized for late-stage alkylations of complex molecules, including pharmaceutical compounds and light-sensitive compounds which degrade under photocatalytic conditions.

Fractionation of lentil seeds (Lens culinaris Medik.) for insecticidal and flavonol tetraglycoside components.

Crude methanol extracts from four cultivated varieties of mature lentil seeds (Lens culinaris Medik.) were found to possess antifeedant and insecticidal properties in laboratory tests with the rice weevil (Sitophilus oryzae L.), an insect pest of stored products. Flash chromatography with silica gel on active Diaion HP-20 methanol extracts gave flavonol, lysolecithin, soyasaponin, and peptide fractions, as determined by HPLC and electrospray ionization LC/MS. The flavonol fraction was shown by high-resolution NMR experiments to contain a mixture of kaempferol 3-O-beta-glucopyranosyl(1-->2)-O-[alpha-rhamnopyranosyl(1-->6)]-beta-galactopyranoside-7-O-alpha-rhamnopyranoside and, tentatively, kaempferol 3-O-beta-glucopyranosyl(1-->2)-O-[alpha-rhamnopyranosyl(1-->6)]-beta-glucopyranoside-7-O-alpha-rhamnopyranoside. These inactive tetraglycosides, although inseparable under the reported HPLC conditions, were detected by NMR spectroscopy in nearly equal proportions. Three lysolecithins were identical to those previously identified in pea extracts. Soyasaponin I (soyasaponin Bb) and soyasaponin VI (soyasaponin betag) were found in Diaion HP-20 methanol extracts. An insecticidal lentil peptide with a mass of 3881 Da, isolated from an Eston variety in small quantities by anion exchange chromatography, was related to the cysteine-rich pea albumin 1b class of botanical insecticides. Binary mixtures of the insecticidal lentil peptide and soybean soyasaponin I were synergistic in tests with S. oryzae.

Adding infection to injury: synergistic effects of predation and parasitism on amphibian malformations.

We explored the importance of interactions between parasite infection and predation in driving an emerging phenomenon of conservation importance: amphibian limb malformations. We suggest that injury resulting from intraspecific predation in combination with trematode infection contributes to the frequency and severity of malformations in salamanders. By integrating field surveys and experiments, we evaluated the individual and combined effects of conspecific attack and parasite (Ribeiroia ondatrae) infection on limb development of long-toed salamanders (Ambystoma macrodactylum). In the absence of Ribeiroia, abnormalities involved missing digits, feet, or limbs and were similar to those produced by cannibalistic attack in experimental trials. At field sites that supported Ribeiroia, malformations were dominated by extra limbs and digits. Correspondingly, laboratory exposure of larval salamanders to Ribeiroia cercariae over a 30-day period induced high frequencies of malformations, including extra digits, extra limbs, cutaneous fusion, and micromelia. However, salamander limbs exposed to both injury and infection exhibited 3-5 times more abnormalities than those exposed to either factor alone. Infection also caused significant delays in limb regeneration and time-to-metamorphosis. Taken together, these results help to explain malformation patterns observed in natural salamander populations while emphasizing the importance of interactions between parasitism and predation in driving disease.

A molecular phylogenetic study of the genus Ribeiroia (Digenea): trematodes known to cause limb malformations in amphibians.

Species of Ribeiroia (Trematoda: Psilostomidae) are known to cause severe limb malformations and elevated mortality in amphibians. However, little is known regarding the number of species in this genus or its relation to other taxa. Species of Ribeiroia have historically been differentiated by slight differences among their larval stages. To better understand the systematics and biogeography of this genus and their potential relevance to the distribution of malformed amphibians, specimens identified as Ribeiroia were collected across much of the known range, including samples from 5 states in the United States (8 sites) and 2 islands in the Caribbean (Puerto Rico and Guadeloupe). A cercaria from East Africa identified as Cercaria lileta (Fain, 1953), with attributes suggestive of Ribeiroia (possibly R. congolensis), was also examined. The intertranscribed spacer region 2 (ITS-2) of the ribosomal gene complex was sequenced and found to consist of 429 nucleotides (nt) for R. ondatrae (United States) and 427 nt for R. marini (Caribbean), with only 6 base differences noted between the 2 species. The ITS-2 region of C. lileta (429 nt) aligned closely with those of the 2 other Ribeiroia species in a phylogenetic analysis that included related trematode genera. This evidence suggests that a third Ribeiroia species exists in tropical Africa. Variation in ITS-2 within R. ondatrae was nonexistent among the 8 populations from North America. Our study further suggests that Ribeiroia spp. originally parasitized Biomphalaria sp., and that a host switch to a closely related snail, Helisoma sp., may have occurred in the lineage represented by R. ondatrae. However, relationships within the Echinostomatidae are not understood well enough to make any robust conclusions at this time.

The interdependent roles of Ca(2+) and cAMP in axon guidance.

Axon guidance is a fundamental process in the developing and regenerating nervous system that is necessary for accurate neuronal wiring and proper brain function. Two of the most important second messengers in axon guidance are Ca(2+) and cAMP. Recently experimental and theoretical studies have uncovered a Ca(2+) - and cAMP-dependent mechanism for switching between attraction and repulsion. Here, we review this process and related Ca(2+) and cAMP interactions, the mechanisms by which necessary intracellular calcium elevations are created, and the pathways, which effect attractive and repulsive responses to the switch.

Diet composition, not calorie intake, rapidly alters intrinsic excitability of hypothalamic AgRP/NPY neurons in mice.

Obesity is a chronic condition resulting from a long-term pattern of poor diet and lifestyle. Long-term consumption of high-fat diet (HFD) leads to persistent activation and leptin resistance in AgRP neurons in the arcuate nucleus of the hypothalamus (ARH). Here, for the first time, we demonstrate acute effects of HFD on AgRP neuronal excitability and highlight a critical role for diet composition. In parallel with our earlier finding in obese, long-term HFD mice, we found that even brief HFD feeding results in persistent activation of ARH AgRP neurons. However, unlike long-term HFD-fed mice, AgRP neurons from short-term HFD-fed mice were still leptin-sensitive, indicating that the development of leptin-insensitivity is not a prerequisite for the increased firing rate of AgRP neurons. To distinguish between diet composition, caloric intake, and body weight, we compared acute and long-term effects of HFD and CD in pair-fed mice on AgRP neuronal spiking. HFD consumption in pair-fed mice resulted in a significant increase in AgRP neuronal spiking despite controls for weight gain and caloric intake. Taken together, our results suggest that diet composition may be more important than either calorie intake or body weight for electrically remodeling arcuate AgRP/NPY neurons.

Amphibian deformities and Ribeiroia infection: an emerging helminthiasis.

Since their widespread appearance in the mid-1990s, malformed amphibians have evoked fear, as well as fascination within the scientific and public communities. Recent evidence from field and laboratory studies has implicated infection by a digenetic trematode--Ribeiroia ondatrae--as an important cause of such deformities. Ribeiroia spp. have a complex life cycle involving planorbid snails, amphibians and water birds. Under natural conditions, malformations might promote parasite transmission by increasing the susceptibility of infected amphibians to predation by definitive hosts. However, with respect to the recent outbreak of deformities, we suggest that exogenous agents (e.g. pesticides, nutrient run-off, introduced fishes) might be interacting with Ribeiroia, resulting in elevated infection levels, and we highlight the need for studies incorporating multiple stressor dynamics to further explore this problem.

Review of the trematode genus Ribeiroia (Psilostomidae): ecology, life history and pathogenesis with special emphasis on the amphibian malformation problem.

Trematodes in the genus Ribeiroia have an indirect life cycle involving planorbid snails as first intermediate hosts, fishes or amphibians as second intermediate hosts and birds or mammals as definitive hosts. Although rarely pathogenic in definitive hosts, Ribeiroia infection can cause severe pathology and mortality in snails and amphibians. This group of parasites has gained notoriety for its prominent rol in the recent rash of amphibian deformities in North America. Under some circumstances, these malformations may enhance parasite transmission by rendering infected amphibian hosts more susceptible to definitive host predators. However, increasing reports of malformations in North American amphibian populations emphasize the importance of understanding infection patterns. Here we review important aspects of the biology, ecology, life cycle and pathogenesis of parasites in the genus Ribeiroia and identify priorities for future research. Based on available morphological descriptions and preliminary molecular data, three species of Ribeiroia are recognized: R. ondatrae in the Americas, R. marini in the Caribbean and R. congolensis/C. lileta in Africa. We further evaluate the influence of abiotic and biotic factors in determining the intensity and prevalence of Ribeiroia infection and malformations in amphibians, highlighting the importance of habitat alteration and secondary factors (e.g. aquatic eutrophication, contaminants) in promoting infection. Although not a "new" parasite, Ribeiroia may have increased in range, prevalence, or intensity in recent years, particularly within amphibian hosts. Nevertheless, while much is known about this intriguing group of parasites, there remains much that we do not know. Particular importance for future research is placed on the following areas: evaluating the phylogenetic position of the genus, establishing the molecular mechanism of parasite-induced malformations in amphibians, isolating the drivers of parasite transmission under field conditions and studying the consequences of malformations for parasite and host populations. Investigation of these questions will benefit enormously from a multidisciplinary approach that effectively integrates parasitology, developmental biology, immunology, herpetology and aquatic ecology.

Insecticidal components from field pea extracts: soyasaponins and lysolecithins.

Extracts from field peas (Pisum sativum L.) have previously been shown to have a utility to control insect pests. To identify potentially new bioinsecticides in field crops, we describe the fractionation of impure extracts (C8 extracts) derived from protein-rich fractions of commercial pea flour. The activity of separated fractions was determined by a flour disk antifeedant bioassay with the rice weevil [Sitophilus oryzae (L.)], an insect pest of stored products. Bioassay-guided fractionation showed that the triterpenoid saponin fractions were partly responsible for the antifeedant activity of C8 extracts. Soyasaponin I (soyasaponin Bb), isolated from peas and soybeans, and mixtures of soyasaponins, comprised of soyasaponins I-III and isolated from soybeans, were inactive antifeedants, but dehydrosoyasaponin I (the C-22 ketone derivative of soyasaponin I), a minor component found in C8 extracts, was shown to be an active component. Dehydrosoyasaponin I (soyasaponin Be) and soyasaponin VI (soyasaponin betag) coeluted under conditions of silica gel thin-layer chromatography and C18 high-performance liquid chromatography. However, dehydrosoyasaponin I could be isolated from saponin-enriched fractions with a reversed phase column of styrene/divinylbenzene operated at alkaline pH. Phospholipids of the lysolecithin type were also identified in saponin fractions of C8 extracts from peas. Three of the lysolecithins were inactive alone against rice weevils, but mixtures of these phospholipids enhanced the insecticidal activity of dehydrosoyasaponin I.