Effect of Silyl Ether Bulk on Excited-State Intramolecular Proton Transfer-Based Sensing of Extant Hydrogen Fluoride for G-Series Nerve Agent Detection.

Luminescence-based sensing provides a method for the rapid detection of nerve agents. Previous approaches have generally focused on sensing materials containing a nucleophilic group that can react with the electrophilic phosphorus atom found in nerve agents. Herein we report an alternative approach for the detection of phosphonofluoridate-based G-series nerve agents that utilizes the fact they contain hydrogen fluoride. We have developed silylated sensing materials based on an excited-state intramolecular proton transfer (ESIPT) reporter compound, 2-[benzo[d]thiazol-2-yl]phenol. Thin films of differently silylated 2-[benzo[d]thiazol-2-yl]phenol were found to react with the hydrogen fluoride found in di-iso-propyl fluorophosphate (DFP), a simulant of sarin (G-series nerve agent), and turn on the ESIPT emission of the reporter compound. The use of the ESIPT emission reduced the impact of background fluorescence and improved the sensitivity of the detection. The effectiveness of the approach was dependent on the stability of the silyl protecting group used, with the least sterically hindered (trimethylsilyl) found to be too unstable to the ambient environment while the most sterically hindered, e.g., tri-iso-propylsilyl and tert-butyldiphenylsilyl were found to be insufficiently reactive to be useful in a real detection scenario. The sensing material composed of the tert-butyl dimethylsilyl protected 2-[benzo[d]thiazol-2-yl]phenol was found to have the best balance between stability under ambient conditions, and reactivity and selectivity to hydrogen fluoride. In a 3 s exposure, it could detect hydrogen fluoride down to a concentration of around 23 ppm in DFP with 99% purity.

Interplay between the Glass Transition Temperature, Analyte Diffusion, and Fluorescence Quenching for Detection of Nitro-Group Containing Explosives Using Organic Semiconducting Films.

Efficient detection of chemical analytes using fluorescence-based sensors necessitates an in-depth understanding of the physical interaction between the analyte molecules and the sensor films. This study explores the interplay between the thermal properties of a series of triphenylamine-centered fluorescent dendrimers with different glass transition temperatures (Tg) for detecting nitroaromatic explosives. When exposed to 4-nitrotoluene (pNT) vapors, biphasic diffusion kinetics were observed for all the dendrimers, corresponding to Super Case II kinetics, suggesting rapid film swelling during initial analyte uptake. The diffusion kinetics were further analyzed using a diffusion-relaxation model, where a strong Tg dependence was observed for both the initial concentration-driven diffusion phase and the slower film relaxation phase. Additionally, a difference in kinetics between analyte uptake and release was observed. The photoluminescence (PL) kinetics also showed a Tg dependence, with more efficient PL recovery observed for films composed of dendrimers that had a lower Tg. Rapid quenching of over 40% with little PL recovery was seen in the dendrimer with the highest Tg (107 °C), while a smaller quench with efficient PL recovery was observed in the dendrimer that had a Tg close to room temperature. The results highlight the critical role of the thermal properties of sensor films in achieving rapid and sensitive detection.

Genomic analysis of NE Atlantic sardine (Sardina pilchardus) reveals reduced variation in a recently established North Sea population and directs reconsideration of management units.

The European sardine (Sardina pilchardus) is under intense fishing pressure and exhibits distributional/abundance shifts linked to environmental change. The current understanding of population demographics needed for sustainable management is uncertain due to concerns that previous genetic studies lacked resolution and limited sampling of sardine north of the Bay of Biscay. To address these issues, we performed mtDNA sequencing and genome wide SNP analysis of samples collected across the Bay of Biscay, Celtic Sea, English Channel and North Sea. The complete SNP data reported a lack of structure throughout the sampled area compatible with high gene flow. A consensus suite of positive outlier SNPs was identified which reported a significant correlation with geographical distance with the largest differentiation between the southern Bay of Biscay and North Sea samples which also reported a significant mtDNA ΦST. While the roles of dispersal limitation and environmental heterogeneity underpinning this require further study, this adds to growing evidence that selection is influencing sardine population structure against a background of high gene flow. The results indicate that while there may be a level of demographic independence between North Sea and South Biscay sardine, the current delimitation of central (Biscay) and northern (Channel and Celtic Sea) operational stocks may misrepresent connectivity between the Biscay and Channel. The North Sea sample exhibited markedly lower mtDNA and nuclear variation than other samples. As sardine have only recently invaded the North Sea such reduced genetic variation is compatible with predictions for peripheral leading-edge populations but contrasts with patterns for other small pelagic species and emphasises the need to consider species-specific genetic structure in ecosystem-based management. Nascent management of the North Sea sardine fishery must ensure that current low levels of genetic diversity are not eroded further as this may decrease the species adaptive potential and inhibit its expansion.

Dilute Donor Organic Solar Cells Based on Non-fullerene Acceptors.

The advent of small molecule non-fullerene acceptor (NFA) materials for organic photovoltaic (OPV) devices has led to a series of breakthroughs in performance and device lifetime. The most efficient OPV devices have a combination of electron donor and acceptor materials that constitute the light absorbing layer in a bulk heterojunction (BHJ) structure. For many BHJ-based devices reported to date, the weight ratio of donor to acceptor is near equal. However, the morphology of such films can be difficult to reproduce and manufacture at scale. There would be an advantage in developing a light harvesting layer for efficient OPV devices that contains only a small amount of either the donor or acceptor. In this work we explore low donor content OPV devices composed of the polymeric donor PM6 blended with high performance NFA materials, Y6 or ITIC-4F. We found that even when the donor:acceptor weight ratio was only 1:10, the OPV devices still have good photoconversion efficiencies of around 6% and 5% for Y6 and ITIC-4F, respectively. It was found that neither charge mobility nor recombination rates had a strong effect on the efficiency of the devices. Rather, the overall efficiency was strongly related to the film absorption coefficient and maintaining adequate interfacial surface area between donor and acceptor molecules/phases for efficient exciton dissociation.

Unlocking the genetic diversity and population structure of the newly introduced two-row spring European HerItage Barley collecTion (ExHIBiT).

In the last century, breeding programs have traditionally favoured yield-related traits, grown under high-input conditions, resulting in a loss of genetic diversity and an increased susceptibility to stresses in crops. Thus, exploiting understudied genetic resources, that potentially harbour tolerance genes, is vital for sustainable agriculture. Northern European barley germplasm has been relatively understudied despite its key role within the malting industry. The European Heritage Barley collection (ExHIBiT) was assembled to explore the genetic diversity in European barley focusing on Northern European accessions and further address environmental pressures. ExHIBiT consists of 363 spring-barley accessions, focusing on two-row type. The collection consists of landraces (~14%), old cultivars (~18%), elite cultivars (~67%) and accessions with unknown breeding history (~1%), with 70% of the collection from Northern Europe. The population structure of the ExHIBiT collection was subdivided into three main clusters primarily based on the accession's year of release using 26,585 informative SNPs based on 50k iSelect single nucleotide polymorphism (SNP) array data. Power analysis established a representative core collection of 230 genotypically and phenotypically diverse accessions. The effectiveness of this core collection for conducting statistical and association analysis was explored by undertaking genome-wide association studies (GWAS) using 24,876 SNPs for nine phenotypic traits, four of which were associated with SNPs. Genomic regions overlapping with previously characterised flowering genes (HvZTLb) were identified, demonstrating the utility of the ExHIBiT core collection for locating genetic regions that determine important traits. Overall, the ExHIBiT core collection represents the high level of untapped diversity within Northern European barley, providing a powerful resource for researchers and breeders to address future climate scenarios.

Genetic analysis of Octopus cyanea reveals high gene flow in the South-West Indian Ocean.

Octopus cyanea (Gray, 1849), abundant in the South-West Indian Ocean (SWIO), constitutes a vital resource for both subsistence and commercial fisheries. However, despite this socioeconomic importance, and recent indications of overfishing, little is known about the population structure of O. cyanea in the region. To inform sustainable management strategies, this study assessed the spatio-temporal population structure and genetic variability of O. cyanea at 20 sites in the SWIO (Kenya, Tanzania, Mozambique, Madagascar, Mauritius, Rodrigues, and the Seychelle Islands) by complementary analysis of mitochondrial DNA (mtDNA) noncoding region (NCR) sequences and microsatellite markers. MtDNA analysis revealed a shallow phylogeny across the region, with demographic tests suggesting historic population fluctuations that could be linked to glacial cycles. Contrary to expectations, NCR variation was comparable to other mtDNA regions, indicating that the NCR is not a hypervariable region. Both nuclear and mtDNA marker types revealed a lack of genetic structure compatible with high gene flow throughout the region. As adults are sedentary, this gene flow likely reflects connectivity by paralarval dispersal. All samples reported heterozygote deficits, which, given the overall absence of structure, likely reflect ephemeral larval recruitment variability. Levels of mtDNA and nuclear variability were similar at all locations and congruent with those previously reported for harvested Octopodidae, implying resilience to genetic erosion by drift, providing current stock sizes are maintained. However, as O. cyanea stocks in the SWIO represent a single, highly connected population, fisheries may benefit from additional management measures, such as rotational closures aligned with paralarval ecology and spanning geopolitical boundaries.

Differentiating Between V- and G-Series Nerve Agent and Simulant Vapours Using Fluorescent Film Responses.

In-field rapid and reliable identification of nerve agents is critical for the protection of Defence and National Security personnel as well as communities. Fluorescence-based detectors can be portable and provide rapid detection of chemical threats. However, most current approaches cannot differentiate between dilute vapors of nerve agent classes and are susceptible to false positives due to the presence of common acids. Here a fluorescence-based method is shown for rapid differentiation between the V-series and phosphonofluoridate G-series nerve agents and avoids false positives due to common acids. Differentiation is achieved through harnessing two different mechanisms. Detection of the V-series is achieved using photoinduced hole transfer whereby the fluorescence of the sensing material is quenched in the presence of the V-series agent. The G-series is detected using a turn-on mechanism in which a silylated excited state intramolecular proton transfer sensing molecule is selectively deprotected by hydrogen fluoride, which is typically found as a contaminant and/or breakdown product in G-series agents such as sarin. The strategy provided discrimination between classes, as the sensor for the G-series agent class is insensitive to the V-series agent, and vice versa, and neither responded to common acids.

Utilizing Different Diffusion Mechanisms for Thin Film Fluorescence-Based Detection and Discrimination of Illicit Drug Vapors.

Film-based fluorescence sensors have been demonstrated to be powerful tools for real-time detection of trace chemical vapors. While explosive vapor detection via fluorescence quenching has been widely explored, fluorescence-based real-time detection and identification of illicit drug vapors remains a challenge. Here, we report two perylene diimide-based sensing materials, P1 and P2, incorporating 2,2-dihexyloctanyl chains and 4-[tris(4-{tert-butyl}phenyl)methyl]phenyl moieties at the imide positions, respectively. Quartz crystal microbalance with in situ photoluminescence measurements showed that N-methylphenethylamine, a simulant of methamphetamine (MA), diffused into films of P1 and P2 via Fickian and case-II mechanisms, respectively. The difference in the analyte diffusion mechanism led to P2 showing significantly faster luminescence quenching but slower luminescence recovery compared to P1. Finally, the different diffusion mechanisms were used as the basis for developing a simple sensor array based on P1 and P2 that could selectively detect free-base illicit drugs (MA, cocaine, and tetrahydrocannabinol) from potential interferants (organic amines, alcohol, and cosmetics) within 40 s.

Fluorinated Cation-Based 2D Perovskites for Efficient and Stable 3D/2D Heterojunction Perovskite Solar Cells.

Three-dimensional (3D) perovskite solar cells (PSCs) containing additives capable of forming two-dimensional (2D) structures in neat films have attracted attention due to their ability to enhance power conversion efficiency (PCE) in combination with improved operational stability. Herein, a newly designed fluorinated ammonium salt, 2-(perfluorophenyl)ethanaminium bromide:chloride50:50 (FEABr:Cl50:50), is introduced into CsMAFAPbI3-based PSCs with a standard n-i-p architecture. FEABr:Cl50:50 was used as an additive in the tin(IV) oxide (SnO2) electron transporting layer (ETL) as well as a surface treatment for the perovskite film. Used in this dual way, the additive was found to passivate charge-trapping defects within the SnO2 ETL and regulate the crystal growth of the perovskite layer. When FEABr:Cl50:50 was deposited onto the surface of the 3D perovskite film, it formed a thin hydrophobic 2D capping layer. Adopting this dual strategy led to the perovskite film having larger grain sizes, improved quality, and overall better device performance. As a result, the best-performing device exhibited a PCE of over 23% with negligible hysteresis in an n-i-p device architecture with an area of 0.2 cm2. Furthermore, unencapsulated devices with the hydrophobic 2D capping layer showed improved stability compared to the control device when measured under continuous light irradiation at a maximum power point (MPP) at 80 ± 5 °C in a humid (≈50%) environment.

Experimentally induced active and quiet sleep engage non-overlapping transcriptional programs in Drosophila.

Sleep in mammals can be broadly classified into two different physiological categories: rapid eye movement (REM) sleep and slow-wave sleep (SWS), and accordingly REM and SWS are thought to achieve a different set of functions. The fruit fly Drosophila melanogaster is increasingly being used as a model to understand sleep functions, although it remains unclear if the fly brain also engages in different kinds of sleep as well. Here, we compare two commonly used approaches for studying sleep experimentally in Drosophila: optogenetic activation of sleep-promoting neurons and provision of a sleep-promoting drug, gaboxadol. We find that these different sleep-induction methods have similar effects on increasing sleep duration, but divergent effects on brain activity. Transcriptomic analysis reveals that drug-induced deep sleep ('quiet' sleep) mostly downregulates metabolism genes, whereas optogenetic 'active' sleep upregulates a wide range of genes relevant to normal waking functions. This suggests that optogenetics and pharmacological induction of sleep in Drosophila promote different features of sleep, which engage different sets of genes to achieve their respective functions.

Perylene Diimide Based Fluorescent Sensors for Drug Simulant Detection: The Effect of Alkyl-Chain Branching on Film Morphology, Exciton Diffusion, Vapor Diffusion, and Sensing Response.

Luminescence-based sensing has been demonstrated to be a powerful method for rapid trace detection of chemical vapors (analytes). Analyte diffusion has been shown to be the critical factor for real-time luminescence-based detection of explosive analytes via photoinduced electron transfer in amorphous films of conjugated polymers and dendrimers. However, similar studies to determine the critical factors for sensing have not been performed on materials that employ photoinduced hole transfer (PHT) to detect low electron affinity analytes such as illicit drugs. Nor have such studies been performed on semicrystalline sensing films. We have developed a family of perylene diimide-based sensing materials capable of undergoing PHT with amine-group containing analytes. It was found that the choice of branched alkyl chain [1-hexylheptyl (PHH), 2-hexyloctyl (PHO), or 2,2-dihexyloctyl (PDHO)] attached to the nitrogen atoms of the imide moiety strongly affected the solution-processed film morphology. PHH and PHO were found to contain crystalline phases, whereas PDHO was essentially amorphous. The degree of crystallinity strongly influenced exciton diffusion, with PHH and PHO exhibiting exciton diffusion coefficients that were 20× and 10× greater than the value of the amorphous PDHO. The degree of film crystallinity was also found to be critical when the films were applied to detect N-methylphenethylamine (MPEA), a simulant of methamphetamine. While PHH had the largest exciton diffusion coefficient [(1.0 ± 0.2) × 10-2 cm2 s-1] and analyte uptake (12.3 ± 1.8 ng) it showed the smallest quenching efficiency (2.6% ng-1). In contrast, PHO, which sorbed the least analyte (6.1 ± 0.4 ng) of the three compounds, had the largest quenching efficiency (7.1% ng-1) due to its molecular packing and hence exciton diffusion coefficient [(4.5 ± 1.4) × 10-3 cm2 s-1] not being affected by sorption of the analyte. These results show that when applying fluorescent films in practical detection scenarios there is a potential trade-off between a high exciton diffusion constant and analyte diffusion for semicrystalline sensing materials and that a high exciton diffusion coefficient in an as-cast film does not necessarily translate into a more efficient fluorescent quenching. The results also show that sensing materials that form semicrystalline films, whose packing is not disrupted by analyte diffusion, provide a route for overcoming these effects and achieving high sensitivity.

Time series DNA barcoding provides insight into factors influencing wood-boring and bark-feeding insect communities in Scots pine, Sitka spruce, and Noble fir stands.

Bark-feeding and wood-boring insect pests can have significant negative impacts on conifers and wood production. The damage they cause is expected to increase in the future due to climate change and the growth of international trade. This study employed DNA barcoding of beetle juveniles (Coleoptera) sampled from standing trap trees and cut log piles at regular intervals over a 2-yr period to monitor the beetle community dynamics and associated environmental factors. Tree species was found to have a major influence on beetle communities, most strikingly at the start of early decay stages. Lower species diversity was reported from standing trap tree samples compared to log pile samples, likely due to higher residual defences in dying and recently dead trees. While the species identified from standing trap trees are more likely to be a threat to the forestry sector, the species found in the log piles are more likely to be beneficial due to their high abundance and their ability to compete with pests for breeding substrate. The analysis of beetles collected inside trees revealed additional information on ontogenetic niches and host preferences beyond that acquired solely from flight interception trap data. Our results offer insights on community composition and dynamics of bark-feeding and wood-boring insect species in Welsh conifer forests and provide resources for monitoring and management of potential pest species.

The impact of film deposition and annealing on the nanostructure and dielectric constant of organic semiconductor thin films.

The strategy of using a bulk-heterojunction light-absorbing layer has led to the most efficient organic solar cells. However, optimising the blend morphology to maximise light absorption, charge generation and extraction can be challenging. Homojunction devices containing a single component have the potential to overcome the challenges associated with bulk heterojunction films. A strategy towards this goal is to increase the dielectric constant of the organic semiconductor to ≈10, which in principle would lead to free charge carrier generation upon photoexcitation. However, the factors that affect the thin film dielectric constants are still not well understood. In this work we report an organic semiconductor material that can be solution processed or vacuum evaporated to form good quality thin films to explore the effect of chromophore structure and film morphology on the dielectric constant and other optoelectronic properties. 2,2'-[(4,4,4',4'-Tetrakis{2-[2-methoxyethoxy]ethyl}-4H,4'H-{2,2'-bi[cyclo-penta[2,1-b:3,4-b']dithiophene]}-6,6'-diyl)bis(methaneylylidene)]dimalononitrile [D(CPDT-DCV)] was designed to have high electron-affinity end groups and low ionisation-potential central moieties. It can be processed from solution or be thermally evaporated, with the film morphology changing from face-on to a herringbone arrangement upon solvent or thermal annealing. The glycol solubilising groups led to the static dielectric constant (taken from capacitance measurements) of the films to be between 6 and 7 (independent of processing conditions), while the optical frequency dielectric constant depended on the processing conditions. The less ordered solution processed film was found to have the lowest optical frequency dielectric constant of 3.6 at 2.0 × 1014 Hz, which did not change upon annealing. In contrast, the more ordered evaporated film had an optical frequency dielectric constant 20% higher at 4.2 and thermal annealing further increased it to 4.5, which is amongst the highest reported for an organic semiconductor at that frequency. Finally, the more ordered evaporated films had more balanced charge transport, which did not change upon annealing.

Sleep deprivation, sleep fragmentation, and social jet lag increase temperature preference in Drosophila.

Despite the fact that sleep deprivation substantially affects the way animals regulate their body temperature, the specific mechanisms behind this phenomenon are not well understood. In both mammals and flies, neural circuits regulating sleep and thermoregulation overlap, suggesting an interdependence that may be relevant for sleep function. To investigate this relationship further, we exposed flies to 12 h of sleep deprivation, or 48 h of sleep fragmentation and evaluated temperature preference in a thermal gradient. Flies exposed to 12 h of sleep deprivation chose warmer temperatures after sleep deprivation. Importantly, sleep fragmentation, which prevents flies from entering deeper stages of sleep, but does not activate sleep homeostatic mechanisms nor induce impairments in short-term memory also resulted in flies choosing warmer temperatures. To identify the underlying neuronal circuits, we used RNAi to knock down the receptor for Pigment dispersing factor, a peptide that influences circadian rhythms, temperature preference and sleep. Expressing UAS-PdfrRNAi in subsets of clock neurons prevented sleep fragmentation from increasing temperature preference. Finally, we evaluated temperature preference after flies had undergone a social jet lag protocol which is known to disrupt clock neurons. In this protocol, flies experience a 3 h light phase delay on Friday followed by a 3 h light advance on Sunday evening. Flies exposed to social jet lag exhibited an increase in temperature preference which persisted for several days. Our findings identify specific clock neurons that are modulated by sleep disruption to increase temperature preference. Moreover, our data indicate that temperature preference may be a more sensitive indicator of sleep disruption than learning and memory.

Ocean warming favours a northern Argyrosomus species over its southern congener, whereas preliminary metabolic evidence suggests that hybridization may promote their adaptation.

Anthropogenic-induced climate change is having profound impacts on aquatic ecosystems, and the resilience of fish populations will be determined by their response to these impacts. The northern Namibian coast is an ocean warming hotspot, with temperatures rising faster than the global average. The rapid warming in Namibia has had considerable impacts on marine fauna, such as the southern extension of the distribution of Argyrosomus coronus from southern Angola into northern Namibian waters, where it now overlaps and hybridizes with the closely related Namibian species, A. inodorus. Understanding how these species (and their hybrids) perform at current and future temperatures is vital to optimize adaptive management for Argyrosomus species. Intermittent flow-through respirometry was used to quantify standard and maximum metabolic rates for Argyrosomus individuals across a range of temperatures. The modelled aerobic scope (AS) of A. inodorus was notably higher at cooler temperatures (12, 15, 18 and 21°C) compared with that of A. coronus, whereas the AS was similar at 24°C. Although only five hybrids were detected and three modelled, their AS was in the upper bounds of the models at 15, 18 and 24°C. These findings suggest that the warming conditions in northern Namibia may increasingly favour A. coronus and promote the poleward movement of the leading edge of their southern distribution. In contrast, the poor aerobic performance of both species at cold temperatures (12°C) suggests that the cold water associated with the permanent Lüderitz Upwelling Cell in the south may constrain both species to central Namibia. This is most concerning for A. inodorus because it may be subjected to a considerable coastal squeeze.

Experimentally induced active and quiet sleep engage non-overlapping transcriptional programs in Drosophila.

Sleep in mammals can be broadly classified into two different physiological categories: rapid eye movement (REM) sleep and slow wave sleep (SWS), and accordingly REM and SWS are thought to achieve a different set of functions. The fruit fly Drosophila melanogaster is increasingly being used as a model to understand sleep functions, although it remains unclear if the fly brain also engages in different kinds of sleep as well. Here, we compare two commonly used approaches for studying sleep experimentally in Drosophila: optogenetic activation of sleep-promoting neurons and provision of a sleep-promoting drug, Gaboxadol. We find that these different sleep-induction methods have similar effects on increasing sleep duration, but divergent effects on brain activity. Transcriptomic analysis reveals that drug-induced deep sleep ('quiet' sleep) mostly downregulates metabolism genes, whereas optogenetic 'active' sleep upregulates a wide range of genes relevant to normal waking functions. This suggests that optogenetics and pharmacological induction of sleep in Drosophila promote different features of sleep, which engage different sets of genes to achieve their respective functions.

Transthyretin Amyloid Cardiomyopathy Risk Evaluation in a Cohort of Patients With Heart Failure.

Introduction Transthyretin amyloid cardiomyopathy (ATTR-CM) is a progressive, infiltrative form of heart failure (HF). Nevertheless, ATTR-CM is a largely underrecognized and misdiagnosed condition. This study's objective was to develop an efficient model to assess the chance of ATTR-CM in patients with HF. Methods This was an observational study of patients with HF who had a confirmed diagnosis of ATTR-CM and those with HF but without known ATTR-CM between January 1, 2019, and July 1, 2021. Patient characteristics were extracted from administrative and claims electronic databases and compared between the groups. A propensity score for having ATTR-CM was modeled. Samples of 50 control patients with the highest and lowest propensity scores were adjudicated to assess whether further workup to evaluate for ATTR-CM was warranted for each patient. The sensitivity and specificity of the model were calculated. Results Thirty-one patients with confirmed ATTR-CM and 7620 patients without known ATTR-CM were included in the study. Patients with ATTR-CM were more likely to be Black and to have atrial flutter/fibrillation, cardiomegaly, HF with preserved ejection fraction, pericardial effusion, carpal tunnel syndrome, joint disorders, and lumbar spinal stenosis and to use a diuretic (all p < 0.05). A propensity model with 16 inputs was developed (c-statistic = 0.875). The model's sensitivity and specificity were 71.9% and 95.2%, respectively. Conclusion The propensity model developed in this study provided an efficient means for identifying patients with HF who are more likely to have ATTR-CM and may warrant further workup.

Twisted Carbazole Dendrons for Solution-Processable Green Emissive Phosphorescent Dendrimers.

A family of first-generation dendrimers containing 3,5-bis(carbazolyl)phenyl dendrons attached to a green emissive fac-tris(2-phenylpyridyl)iridium(III) core were prepared. The solubility of the dendrimers was imparted by the attachment of tert-butyl surface groups to the carbazole moieties. The dendrimers differed in the number of dendrons attached to each ligand (one or two dendrons) as well as the degree of rotational restriction within the dendrons. The densities of the films containing the doubly dendronized materials were higher than those of their mono-dendronized counterparts, with the dendrimer containing two rotationally constrained dendrons per ligand having the highest density at 1.12 ± 0.04 g cm-3. The dendrimers were found to have high photoluminescence quantum yields (PLQYs) in solution of between 80 and 90%, with the doubly dendronized materials having the lower values and a red-shifted emission. The neat film PLQY values of the dendrimers were less than those measured in solution although the relative decrease was smaller for the doubly dendronized materials. The dendrimers were incorporated into solution-processed bilayer organic light-emitting diodes (OLEDs) composed of neat or blend emissive layers and an electron transport layer. The best-performing devices had the dendrimers blended with a host material and external quantum efficiencies as high as 14.0%, which is higher than previously reported results for carbazole-incorporating emissive dendrimers. A feature of the devices containing blends of the doubly dendronized materials was that the maximum efficiency was relatively insensitive to the concentration in the host between 1 and 7 mol %.

A highly sensitive LC-MS/MS method for quantitative determination of 7 vitamin D metabolites in mouse brain tissue.

Despite its critical role in neurodevelopment and brain function, vitamin D (vit-D) homeostasis, metabolism, and kinetics within the central nervous system remain largely undetermined. Thus, it is of critical importance to establish an accurate, highly sensitive, and reproducible method to quantitate vit-D in brain tissue. Here, we present a novel liquid chromatography tandem mass spectrometry (LC-MS/MS) method and for the first time, demonstrate detection of seven major vit-D metabolites in brain tissues of C57BL/6J wild-type mice, namely 1,25(OH)2D3, 3-epi-1,25(OH)2D3, 1,25(OH)2D2, 25(OH)D3, 25(OH)D2, 24,25(OH)2D3, and 24,25(OH)2D2. Chromatographic separation was achieved on a pentaflurophenyl column with 3 mM ammonium formate water/methanol [A] and 3 mM ammonium formate methanol/isopropanol [B] mobile phase components. Detection was by positive ion electrospray tandem mass spectrometry with the EVOQ elite triple quadrupole mass spectrometer with an Advance ultra-high-performance liquid chromatograph and online extraction system. Calibration standards of each metabolite prepared in brain matrices were used to validate the detection range, precision, accuracy, and recovery. Isotopically labelled analogues, 1,25(OH)2D3-d3, 25(OH)D3-c5, and 24,25(OH)2D3-d6, served as the internal standards for the closest molecular-related metabolite in all measurements. Standards between 1 fg/mL and 10 ng/mL were injected with a resulting linear range between 0.001 and 1 ng, with an LLOD and LLOQ of 1 pg/mL and 12.5 pg/mL, respectively. The intra-/inter-day precision and accuracy for measuring brain vit-D metabolites ranged between 0.12-11.53% and 0.28-9.11%, respectively. Recovery in acetonitrile ranged between 99.09 and 106.92% for all metabolites. Collectively, the sensitivity and efficiency of our method supersedes previously reported protocols used to measure vit-D and to our knowledge, the first protocol to reveal the abundance of 25(OH)D2, 1,25(OH)D2, and 24,25(OH)2D2, in brain tissue of any species. This technique may be important in supporting the future advancement of pre-clinical research into the function of vit-D in neurophysiological and neuropsychiatric disorders, and neurodegeneration.