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The movements that give rise to the body's structure are powered by cell shape changes and rearrangements that are coordinated at supracellular scales. How such cellular coordination arises and integrates different morphogenetic programs is unclear. Using quantitative imaging, we found a complex pattern of adherens junction (AJ) levels in the ectoderm prior to gastrulation onset in Drosophila. AJ intensity exhibited a double-sided gradient, with peaks at the dorsal midline and ventral neuroectoderm. We show that this dorsal-ventral AJ pattern is regulated by epidermal growth factor (EGF) signaling and that this signal is required for ectoderm cell movement during mesoderm invagination and axis extension. We identify AJ levels and junctional actomyosin as downstream effectors of EGFR signaling. Overall, our study demonstrates an EGF-patterned mechanical feedback mechanism that coordinates tissue folding and convergent extension to facilitate embryo-wide gastrulation movements., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2024 Elsevier Inc. All rights reserved.)

A continuous flow process has been developed for the defluorosilylation of trifluoromethane (HFC-23) and 2,3,3,3-tetrafluoropropene (HFO-1234yf) through reaction with lithium silanide reagents under inert conditions. Design of experiment optimization improved process conditions, including productivity, yields, reduction of solvent use, and gas destruction. The small chain fluorinated organosilane products R 3 SiCF 2 H and R 3 SiCH 2 C(F)═CF 2 were competent nucleophiles in the fluoride-catalyzed difluoromethylation of aldehydes, and trifluoroallylation of aldehydes, ketones, and imines.

During vertebrate organogenesis, increases in morphological complexity are tightly coupled to morphogen expression. In this work, we studied how morphogens influence self-organizing processes at the collective or "supra"-cellular scale in avian skin. We made physical measurements across length scales, which revealed morphogen-enabled material property differences that were amplified at supracellular scales in comparison to cellular scales. At the supracellular scale, we found that fibroblast growth factor (FGF) promoted "solidification" of tissues, whereas bone morphogenetic protein (BMP) promoted fluidity and enhanced mechanical activity. Together, these effects created basement membrane-less compartments within mesenchymal tissue that were mechanically primed to drive avian skin tissue budding. Understanding this multiscale process requires the ability to distinguish between proximal effects of morphogens that occur at the cellular scale and their functional effects, which emerge at the supracellular scale.

Vertebrate groups have evolved strikingly diverse color patterns. However, it remains unknown to what extent the diversification of such patterns has been shaped by the proximate, developmental mechanisms that regulate their formation. While these developmental mechanisms have long been inaccessible empirically, here we take advantage of recent insights into rodent pattern formation to investigate the role of development in shaping pattern diversification across rodents. Based on a broad survey of museum specimens, we first establish that various rodents have independently evolved diverse patterns consisting of longitudinal stripes, varying across species in number, color, and relative positioning. We then interrogate this diversity using a simple model that incorporates recent molecular and developmental insights into stripe formation in African striped mice. Our results suggest that, on the one hand, development has facilitated pattern diversification: The diversity of patterns seen across species can be generated by a single developmental process, and small changes in this process suffice to recapitulate observed evolutionary changes in pattern organization. On the other hand, development has constrained diversification: Constraints on stripe positioning limit the scope of evolvable patterns, and although pattern organization appears at first glance phylogenetically unconstrained, development turns out to impose a cryptic constraint. Altogether, this work reveals that pattern diversification in rodents can in part be explained by the underlying development and illustrates how pattern formation models can be leveraged to interpret pattern evolution.

Recreational angling is a very popular outdoor activity that is weather-dependent, although investigations of this relationship are rare. This study used weekly fishing effort (2015-2021) estimates throughout coastal Louisiana to understand how effort changed in response to weather conditions. Although we found evidence for some effect of all the weather variables, temperature reported the greatest number of monthly effects, along with an overall declining effect throughout the year. We also examined how tropical storms and hurricanes reduce fishing effort, but that effort recovers rapidly after the storm. Finally, we examined fishing effort during the first year of the pandemic (2020) compared to previous years and found some monthly increases exceeding 100% of normal effort. Understanding angler motivations remains an important part of fishery management, and in a future with changes to weather, hurricanes, and global health crises, we can now know more about how environmental factors change angling effort., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2023 Midway, Miller. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Four-membered heterocycles offer exciting potential as small polar motifs in medicinal chemistry but require further methods for incorporation. Photoredox catalysis is a powerful method for the mild generation of alkyl radicals for C-C bond formation. The effect of ring strain on radical reactivity is not well understood, with no studies that address this question systematically. Examples of reactions that involve benzylic radicals are rare, and their reactivity is challenging to harness. This work develops a radical functionalization of benzylic oxetanes and azetidines using visible light photoredox catalysis to prepare 3-aryl-3-alkyl substituted derivatives and assesses the influence of ring strain and heterosubstitution on the reactivity of small-ring radicals. 3-Aryl-3-carboxylic acid oxetanes and azetidines are suitable precursors to tertiary benzylic oxetane/azetidine radicals which undergo conjugate addition into activated alkenes. We compare the reactivity of oxetane radicals to other benzylic systems. Computational studies indicate that Giese additions of unstrained benzylic radicals into acrylates are reversible and result in low yields and radical dimerization. Benzylic radicals as part of a strained ring, however, are less stable and more π-delocalized, decreasing dimer and increasing Giese product formation. Oxetanes show high product yields due to ring strain and Bent's rule rendering the Giese addition irreversible.

Objective: Frontline mental health, emergency, law enforcement, and social workers have faced unprecedented psychological distress in responding to the COVID-19 pandemic. The purpose of the RCT (Randomized Controls Trial) study was to investigate the effectiveness of a Group EMDR (Eye Movement Desensitization and Reprocessing) therapy (Group Traumatic Episode Protocol-GTEP) in the treatment of Post-Traumatic Stress Disorder (PTSD) and Moral Injury. The treatment focus is an early intervention, group trauma treatment, delivered remotely as video-conference psychotherapy (VCP). This early intervention used an intensive treatment delivery of 4x2h sessions over 1-week. Additionally, the group EMDR intervention utilized therapist rotation in treatment delivery., Methods: The study's design comprised a delayed (1-month) treatment intervention (control) versus an active group. Measurements included the International Trauma Questionnaire (ITQ), Generalized Anxiety Disorder Assessment (GAD-7), Patient Health Questionnaire (PHQ-9), Moral Injury Events Scale (MIES), and a Quality-of-Life psychometric (EQ-5D), tested at T0, T1: pre-treatment, T2: post-treatment, T3: 1-month follow-up (FU), T4: 3-month FU, and T5: 6-month FU. The Adverse Childhood Experiences - International version (ACEs), Benevolent Childhood Experience (BCEs) was ascertained at pre-treatment only. N  = 85 completed the study., Results: Results highlight a significant treatment effect within both active and control groups. Post Hoc comparisons of the ITQ demonstrated a significant difference between T1 pre (mean 36.8, SD 14.8) and T2 post (21.2, 15.1) (t11.58) = 15.68, p  < 0.001). Further changes were also seen related to co-morbid factors. Post Hoc comparisons of the GAD-7 demonstrated significant difference between T1 pre (11.2, 4.91) and T2 post (6.49, 4.73) ( t  = 6.22) = 4.41, p  < 0.001; with significant difference also with the PHQ-9 between T1 pre (11.7, 5.68) and T2 post (6.64, 5.79) ( t  = 6.30) = 3.95, p  < 0.001, d  = 0.71. The treatment effect occurred irrespective of either ACEs/BCEs during childhood. However, regarding Moral Injury, the MIES demonstrated no treatment effect between T1 pre and T5 6-month FU. The study's findings discuss the impact of Group EMDR therapy delivered remotely as video-conference psychotherapy (VCP) and the benefits of including a therapist/rotation model as a means of treatment delivery. However, despite promising results suggesting a large treatment effect in the treatment of trauma and adverse memories, including co-morbid symptoms, research results yielded no treatment effect in frontline/emergency workers in addressing moral injury related to the COVID-19 pandemic., Conclusion: The NICE (2018) guidance on PTSD highlighted the paucity of EMDR therapy research used as an early intervention. The primary rationale for this study was to address this critical issue. In summary, treatment results for group EMDR, delivered virtually, intensively, using therapist rotation are tentatively promising, however, the moral dimensions of trauma need consideration for future research, intervention development, and potential for further scalability. The data contributes to the emerging literature on early trauma interventions. Clinical Trial Registration: Clinicaltrials.gov, ISRCTN16933691., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Farrell, Moran, Zat, Miller, Knibbs, Papanikolopoulos, Prattos, McGowan, McLaughlin, Barron, Mattheß and Kiernan.)

The tropospheric circumpolar vortex (CPV), an important signature of processes steering the general atmospheric circulation, surrounds each pole and is linked to the surface weather conditions. The CPV can be characterized by its area and circularity ratio ( R c ), which both vary temporally. This research advances previous work identifying the daily 500-hPa Northern Hemispheric CPV (NHCPV) area, R c , and temporal trends in its centroid by examining linear trends and periodic cycles in NHCPV area and R c (1979-2017). Results suggest that NHCPV area has increased linearly over time. However, a more representative signal of the planetary warming may be the temporally weakening gradient which has blurred NHCPV distinctiveness-perhaps a new indicator of Arctic amplification. R c displays opposing trends in subperiods and an insignificant overall trend. Distinct annual and semiannual cycles exist for area and R c over all subperiods. These features of NHCPV change over time may impact surface weather/climate., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Bushra, Rohli, Li, Miller and Mostafiz.)

Rhenium-based metallodrugs have recently been highlighted as promising candidates for new antibiotics to combat multi-drug resistant (MDR) pathogens. A new class of rhenium(V) dioxo complexes were prepared from readily accessible diphosphine ligands, and have been shown to possess potent activity against Staphylococcus aureus ( S. aureus ) and Candida albicans ( C. albicans ) alongside low human cell toxicity.

How does breaking the symmetry of an equation alter the symmetry of its solutions? Here, we systematically examine how reducing underlying symmetries from spherical to axisymmetric influences the dynamics of an archetypal model of cell polarization, a key process of biological spatial self-organization. Cell polarization is characterized by nonlinear and non-local dynamics, but we overcome the theory challenges these traits pose by introducing a broadly applicable numerical scheme allowing us to efficiently study continuum models in a wide range of geometries. Guided by numerical results, we discover a dynamical hierarchy of timescales that allows us to reduce relaxation to a purely geometric problem of area-preserving geodesic curvature flow. Through application of variational results, we analytically construct steady states on a number of biologically relevant shapes. In doing so, we reveal non-trivial solutions for symmetry breaking., Competing Interests: Competing interests The authors declare no competing interests.

N-Triphos derivatives (NP 3 R , R = alkyl, aryl) and asymmetric variants (NP 2 R X R' , R' = alkyl, aryl, X = OH, NR 2 , NRR') are an underexplored class of tuneable, tripodal ligands in relation to the coordination chemistry of Re and Tc for biomedical applications. Mixed-ligand approaches are a flexible synthetic route to obtain Tc complexes of differing core structures and physicochemical properties. Reaction of the NP 3 Ph ligand with the Re(V) oxo precursor [ReOCl 3 (PPh 3 ) 2 ] generated the bidentate complex [ReOCl 3 (κ 2 -NP 2 Ph OH Ar )], which possesses an unusual AA'BB'XX' spin system with a characteristic second-order NMR lineshape that is sensitive to the bi- or tridentate nature of the coordinating diphosphine unit. The use of the asymmetric NP 2 Ph OH Ar ligand resulted in the formation of both bidentate and tridentate products depending on the presence of base. The tridentate Re(V) complex [ReOCl 2 (κ 3 -NP 2 Ph O Ar )] has provided the basis of a new reactive "metal-fragment" for further functionalization in [3 + 2] mixed-ligand complexes. The synthesis of [3 + 2] complexes with catechol-based π-donors could also be achieved under one-pot, single-step conditions from Re(V) oxo precursors. Analogous complexes can also be synthesized from suitable 99 Tc(V) precursors, and these complexes have been shown to exhibit highly similar structural properties through spectroscopic and chromatographic analysis. However, a tendency for the {M V O} 3+ core to undergo hydrolysis to the {M V O 2 } + core has been observed both in the case of M = Re and markedly for M = 99 Tc complexes. It is likely that controlling this pathway will be critical to the generation of further stable Tc(V) derivatives.

A novel radiolabelling method exploiting 11 C-dithiocarbamate ligands has been used to generate 11 C-labelled Au(I), Au(III), Pd(II) and Pt(II) complexes in high radiochemical yields (71-99%). Labelled complexes were prepared in a rapid one-pot procedure via the substitution reaction of 11 C-dithiocarbamate ligands with appropriate transition metal chloride precursors.

Background: Pre-term or full-term childbirth can be experienced as physically or psychologically traumatic. Cumulative and trans-generational effects of traumatic stress on both psychological and physical health indicate the ethical requirement to investigate appropriate preventative treatment for stress symptoms in women following a routine traumatic experience such as childbirth., Objective: The objective of this review was to investigate the effectiveness of early psychological interventions in reducing or preventing post-traumatic stress symptoms and post-traumatic stress disorder in post-partum women within twelve weeks of a traumatic birth., Methods: Randomised controlled trials and pilot studies of psychological interventions preventing or reducing post-traumatic stress symptoms or PTSD, that included women who had experienced a traumatic birth, were identified in a search of Cochrane Central Register of Randomised Controlled Trials, MEDLINE, Embase, Psychinfo, PILOTS, CINAHL and Proquest Dissertations databases. One author performed database searches, verified results with a subject librarian, extracted study details and data. Five authors appraised extracted data and agreed upon risk of bias. Analysis was completed with Rev Man 5 software and quality of findings were rated according to Grading of Recommendation, Assessment, Development, and Evaluation., Results: Eleven studies were identified that evaluated the effectiveness of a range of early psychological interventions. There was firm evidence to suggest that midwifery or clinician led early psychological interventions administered within 72 hours following traumatic childbirth are more effective than usual care in reducing traumatic stress symptoms in women at 4-6 weeks. Further studies of high methodological quality that include longer follow up of 6-12 months are required in order to substantiate the evidence of the effectiveness of specific face to face and online early psychological intervention modalities in preventing the effects of stress symptoms and PTSD in women following a traumatic birth before introduction to routine care and practice., Prospero Registration: CRD42020202576, https://www.crd.york.ac.uk/prospero/display&#95;record.php?RecordID=202576., Competing Interests: I have read the journal’s policy and the authors of this manuscript have the following competing interests: PWM is clinical lead for Mirabilis health a private trauma-focused mental health service, which provides pro bono psychotherapy to participants for research projects. PWM provides EMDR training as a part of Mirabilis Health Academy. PWM is a member by invitation of the Council of Scholars; part of the Future of EMDR Therapy Project. The Project works on developing global EMDR standards for training and competency benchmarking guidelines in EMDR therapy. ES is the developer of the EMDR G-TEP protocol and provides training workshops for EMDR clinicians and is also a member of the Council of Scholars.

Braiding of topological structures in complex matter fields provides a robust framework for encoding and processing information, and it has been extensively studied in the context of topological quantum computation. In living systems, topological defects are crucial for the localization and organization of biochemical signaling waves, but their braiding dynamics remain unexplored. Here, we show that the spiral wave cores, which organize the Rho-GTP protein signaling dynamics and force generation on the membrane of starfish egg cells, undergo spontaneous braiding dynamics. Experimentally measured world line braiding exponents and topological entropy correlate with cellular activity and agree with predictions from a generic field theory. Our analysis further reveals the creation and annihilation of virtual quasi-particle excitations during defect scattering events, suggesting phenomenological parallels between quantum and living matter., Competing Interests: The authors declare no competing interest.

During January-February 2020, parts of China faced restricted mobility under COVID-19 quarantines, which have been associated with improved air quality. Because particulate pollutants scatter, diffuse, and absorb incoming solar radiation, a net negative radiative forcing, decreased air pollution can yield surface warming. As such, this study (1) documents the evolution of China's January-February 2020 air temperature and concurrent particulate changes; (2) determines the temperature response related to reduced particulates during the COVID-19 quarantine (C19Q); and (3) discusses the conceptual implications for temperature-dependent disease transmission. C19Q particulate evolution is monitored using satellite analyses, and concurrent temperature anomalies are diagnosed using surface stations and Aqua AIRS imagery. Meanwhile, two WRF-Chem simulations are forced by normal emissions and the satellite-based urban aerosol changes, respectively. Urban aerosols decreased from 27.1% of pre-C19Q aerosols to only 17.5% during C19Q. WRF-Chem resolved ~0.2 °C warming across east-central China, that represented a minor, though statistically significant contribution to C19Q temperature anomalies. The largest area of warming is concentrated south of Chengdu and Wuhan where temperatures increased between +0.2-0.3 °C. The results of this study are important for understanding the anthropogenic forcing on regional meteorology. Epidemiologically, the marginal, yet persistent, warming during C19Q may retard temperature-dependent disease transmission, possibly including SARS-CoV-2., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Background: Uveal melanoma (UVM) is a rare cancer that shows sex difference in incidence and survival, with little previous report for the underlying mechanism., Methods: This study used the SEER data (1974-2016) for an age-dependent analysis on sex difference in UVM, and further used the TCGA-UVM genomics dataset for analyzing the differential gene expression profiles in tumors from men and women., Results: Our results demonstrate a sex difference in older age (≥40 years) but not in younger patients, with men exhibiting a higher incidence rate than women. However, younger women have shown a continuous increasing trend since 1974. Examining the 11 major oncogenes and tumor suppressors in UVM revealed that EIF1AX showed a significant sex difference in mRNA accumulation and copy number variation, with female tumors expressing higher levels of EIF1AX and exhibiting more variations in copy numbers. EIF1AX mRNA levels were significantly inversely correlated with EIF1AX copy numbers in female tumors only, but not in male tumors. Differential gene expression analysis at the whole genomic level identified a set of 92 protein-coding and 16 RNA-coding genes which exhibited differential expression in men and women (fold of change cutoff at 1.7, adjusted p value < 0.05, FDR < 0.05). Network analysis showed significant difference in immune response and in disulfide bond formation, with EGR1/EGR2 and PDIA2 genes as regulators for immune response and disulfide bond formation, respectively. The melanocortin pathway which is linked to both melanin synthesis and obesity seems to be altered with unclear significance, as the sex difference in POMC, DCT/TYRP2, and MRAP2 was observed but with no clear direction., Conclusion: This study reveals possible mechanisms for the sex difference in tumorigenesis of UVM which has potentials for better understanding and prevention of UVM.

The Ccr4-Not complex functions as an effector of multiple signaling pathways that control gene transcription and mRNA turnover. Consequently, Ccr4-Not contributes to a diverse array of processes, which includes a significant role in cell metabolism. Yet a mechanistic understanding of how it contributes to metabolism is lacking. Herein, we provide evidence that Ccr4-Not activates nutrient signaling through the essential target of rapamycin complex 1 (TORC1) pathway. Ccr4-Not disruption reduces global TORC1 signaling, and it also upregulates expression of the cell wall integrity (CWI) pathway terminal kinase Mpk1. Although CWI signaling represses TORC1 signaling, we find that Ccr4-Not loss inhibits TORC1 independently of CWI activation. Instead, we demonstrate that Ccr4-Not promotes the function of the vacuole V-ATPase, which interacts with the Gtr1 GTPase-containing EGO complex to stimulate TORC1 in response to nutrient sufficiency. Bypassing the V-ATPase requirement in TORC1 activation using a constitutively active Gtr1 mutant fully restores TORC1 signaling in Ccr4-Not deficient cells. Transcriptome analysis and functional studies revealed that loss of the Ccr4 subunit activates the TORC1 repressed retrograde signaling pathway to upregulate mitochondrial activity. Blocking this mitochondrial upregulation in Ccr4-Not deficient cells further represses TORC1 signaling, and it causes synergistic deficiencies in mitochondrial-dependent metabolism. These data support a model whereby Ccr4-Not loss impairs V-ATPase dependent TORC1 activation that forces cells to enhance mitochondrial metabolism to sustain a minimal level of TORC1 signaling necessary for cell growth and proliferation. Therefore, Ccr4-Not plays an integral role in nutrient signaling and cell metabolism by promoting V-ATPase dependent TORC1 activation., Competing Interests: The authors have declared that no competing interests exist.

Differential scanning calorimetry (DSC) is increasingly used as evidence to support a favourable safety profile of novel chemistry, or to highlight the need for caution. DSC enables preliminary assessment of the thermal hazards of a potentially energetic compound. However, unlike other standard characterisation methods, which have well defined formats for reporting data, the current reporting of DSC results for thermal hazard assessment has shown concerning trends. Around half of all results in 2019 did not include experimental details required to replicate the procedure. Furthermore, analysis for thermal hazard assessment is often only conducted in unsealed crucibles, which could lead to misleading results and dangerously incorrect conclusions. We highlight the specific issues with DSC analysis of hazardous compounds currently in the organic chemistry literature and provide simple "best practice" guidelines which will give chemists confidence in reported DSC results and the conclusions drawn from them., (© 2020 Wiley-VCH GmbH.)

Epilepsy affects millions of individuals worldwide and many cases are pharmacoresistant. Duplication 15q syndrome (Dup15q) is a genetic disorder caused by duplications of the 15q11.2-q13.1 region. Phenotypes include a high rate of pharmacoresistant epilepsy. We developed a Dup15q model in Drosophila melanogaster that recapitulates seizures in Dup15q by over-expressing fly Dube3a or human UBE3A in glial cells, but not neurons, implicating glia in the Dup15q epilepsy phenotype. We compared Dube3a overexpression in glia (repo>Dube3a) versus neurons (elav>Dube3a) using transcriptomics and proteomics of whole fly head extracts. We identified 851 transcripts differentially regulated in repo>Dube3a, including an upregulation of glutathione S-transferase (GST) genes that occurred cell autonomously within glial cells. We reliably measured approximately 2,500 proteins by proteomics, most of which were also quantified at the transcript level. Combined transcriptomic and proteomic analysis revealed an enrichment of 21 synaptic transmission genes downregulated at the transcript and protein in repo>Dube3a indicating synaptic proteins change in a cell non-autonomous manner in repo>Dube3a flies. We identified 6 additional glia originating bang-sensitive seizure lines and found upregulation of GSTs in 4 out of these 6 lines. These data suggest GST upregulation is common among gliopathic seizures and may ultimately provide insight for treating epilepsy., Competing Interests: Declaration of Competing Interest None., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

Inspired by the robust locomotion of limbless animals in a range of environments, the development of soft robots capable of moving by localized swelling, bending, and other forms of differential growth has become a target for soft matter research over the last decade. Engineered soft robots exhibit a wide range of morphologies, but theoretical investigations of soft robot locomotion have largely been limited to slender bodied or one-dimensional examples. Here, we demonstrate design principles regarding the locomotion of two-dimensional soft materials driven by morphoelastic waves along a dry substrate. Focusing on the essential common aspects of many natural and man-made soft actuators, a continuum model is developed which links the deformation of a thin elastic sheet to surface-bound excitation waves. Through a combination of analytic and numerical methods, we investigate the relationship between induced active stress and self-propulsion performance of self-propelling sheets driven by FitzHugh-Nagumo type chemical waves. Examining the role of both sheet geometry and terrain geography on locomotion, our results can provide guidance for the design of more efficient soft crawling devices.

Despite their wide use in academia as metal-carbene precursors, diazo compounds are often avoided in industry owing to concerns over their instability, exothermic decomposition, and potential explosive behavior. The stability of sulfonyl azides and other diazo transfer reagents is relatively well understood, but there is little reliable data available for diazo compounds. This work first collates available sensitivity and thermal analysis data for diazo transfer reagents and diazo compounds to act as an accessible reference resource. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and accelerating rate calorimetry (ARC) data for the model donor/acceptor diazo compound ethyl (phenyl)diazoacetate are presented. We also present a rigorous DSC dataset with 43 other diazo compounds, enabling direct comparison to other energetic materials to provide a clear reference work to the academic and industrial chemistry communities. Interestingly, there is a wide range of onset temperatures ( T onset ) for this series of compounds, which varied between 75 and 160 °C. The thermal stability variation depends on the electronic effect of substituents and the amount of charge delocalization. A statistical model is demonstrated to predict the thermal stability of differently substituted phenyl diazoacetates. A maximum recommended process temperature ( T D24 ) to avoid decomposition is estimated for selected diazo compounds. The average enthalpy of decomposition (Δ H D ) for diazo compounds without other energetic functional groups is -102 kJ mol -1 . Several diazo transfer reagents are analyzed using the same DSC protocol and found to have higher thermal stability, which is in general agreement with the reported values. For sulfonyl azide reagents, an average Δ H D of -201 kJ mol -1 is observed. High-quality thermal data from ARC experiments shows the initiation of decomposition for ethyl (phenyl)diazoacetate to be 60 °C, compared to that of 100 °C for the common diazo transfer reagent p -acetamidobenzenesulfonyl azide ( p -ABSA). The Yoshida correlation is applied to DSC data for each diazo compound to provide an indication of both their impact sensitivity (IS) and explosivity. As a neat substance, none of the diazo compounds tested are predicted to be explosive, but many (particularly donor/acceptor diazo compounds) are predicted to be impact-sensitive. It is therefore recommended that manipulation, agitation, and other processing of neat diazo compounds are conducted with due care to avoid impacts, particularly in large quantities. The full dataset is presented to inform chemists of the nature and magnitude of hazards when using diazo compounds and diazo transfer reagents. Given the demonstrated potential for rapid heat generation and gas evolution, adequate temperature control and cautious addition of reagents that begin a reaction are strongly recommended when conducting reactions with diazo compounds., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Tissue morphogenesis is strikingly robust. Yet, how tissues are sculpted under challenging conditions is unknown. Here, we combined network analysis, experimental perturbations, and computational modeling to determine how network connectivity between hundreds of contractile cells on the ventral side of the Drosophila embryo ensures robust tissue folding. We identified two network properties that mechanically promote robustness. First, redundant supracellular cytoskeletal network paths ensure global connectivity, even with network degradation. By forming many more connections than are required, morphogenesis is not disrupted by local network damage, analogous to the way redundancy guarantees the large-scale function of vasculature and transportation networks. Second, directional stiffening of edges oriented orthogonal to the folding axis promotes furrow formation at lower contractility levels. Structural redundancy and directional network stiffening ensure robust tissue folding with proper orientation., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The cobalt dinitrogen complexes [{(EP3Ph)Co(μ-N2)}2Mg(THF)4], with triphos ligand scaffolds (EP3Ph, E = N or CMe), were prepared via two electron reductions of the Co(i) precursors [CoCl(EP3Ph)]. Both complexes showed high degrees of N2 activation owing to the formation of a rare M-NN-Mg-NN-M bridging-magnesium core. These systems showed further N2 functionalisation reactivity by silylation, forming silyldiazenido complexes [(EP3Ph)Co(NNSiMe3)].

Searching for porous materials that can be employed as solid stationary phases for chromatographic separations, porous membrane matrixes and solid supports for catalysis has become an active research area. Strategies for embedding emerging porous materials in columnar systems and their subsequent applications (separation and catalysis) have been developed, which benefit from the remarkable progress in the discovery and development of porous materials based on metal-organic coordination or dynamic covalent bonding such as metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), porous organic cages, and porous organic polymers. In this review, porous materials that have been confined within capillary columns as packed, monolithic and open tubular columns are discussed. Progress in chromatographic separation and continuous flow catalytic synthesis is reviewed according to three major strategies. Applications of porous materials in membrane-separation fibre membrane systems and microfluidic devices with various functions are also highlighted.

2-Azido-4,6-dimethoxy-1,3,5-triazine (ADT) was reported recently as a new "intrinsically safe" diazo-transfer reagent. This assessment was based on differential scanning calorimetry data indicating that ADT exhibits endothermic decomposition. We present DSC data on ADT that show exothermic decomposition with an initiation temperature ( T init ) of 159 °C and an enthalpy of decomposition (Δ H D ) of -1135 J g -1 (-207 kJ mol -1 ). We conclude that ADT is potentially explosive and must be treated with caution, being of comparable exothermic magnitude to tosyl azide (TsN 3 ). A maximum recommended process temperature for ADT is 55 °C.

El Yunque National Forest, situated in the Luquillo Mountains of northeast Puerto Rico, is home to a wide range of climate-sensitive ecosystems and forest types. In particular, these ecosystems are highly sensitive to changes in the hydroclimate, even on short time scales. Current global climate models (GCMs) predict coarse-scale reductions in precipitation across the Caribbean prompting the need to investigate future fine-scale hydroclimate variability in the Luquillo Mountains. This research downscales coarse-resolution GCM RCP8.5 predictions from the IPCC CMIP5 project to the local scale to better assess future rainfall variability during the most critical period of the annual hydroclimate cycle, the early rainfall season (ERS). An artificial neural network (ANN) is developed using five field variables (1000-, 850-, 700-, and 500-hPa specific humidity and 1000-700-hPa bulk wind shear) and four derived precipitation forecasting parameters from the ERA-Interim reanalysis. During the historical period (1985-2016), the ANN predicts a binary dry (<5 mm) versus wet (≥5 mm) day outcome with 92% percent accuracy. When the historical inputs are replaced with bias-corrected data from four CMIP5 GCMs, the downscaled ensemble mean indicates a 7.2% increase in ERS dry-day frequency by mid-century (2041-2060), yielding an ERS dry-day percentage of 70% by mid-century. The results presented here show that the decrease in precipitation and wet-days is, at least in part, due to an increase in 1000-700 hPa bulk wind shear and a less favorable thermodynamic environment driven by increased mid-tropospheric warming and a stronger trade wind inversion. By regressing ERS total precipitation against dry-day frequency (R 2  = 0.95), the predicted mid-century dry-day proportion corresponds to a ~200-mm decrease in seasonal precipitation. In contrast, the ensemble predicts a dry-day frequency recovery back towards the historical climatological mean by end-century (2081-2100)., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Multiplex PCR combined with a pharmacist-driven reporting protocol was compared to the standard of care within a community hospital to evaluate initial changes after notification of a positive blood culture. The intervention group demonstrated decreased times to changes in antimicrobial therapy ( P  = 0.0081), increased changes to optimal antimicrobial therapy ( P  = 0.013), and decreased vancomycin use for coagulase-negative staphylococcus contaminants ( P  < 0.01) with multiplex PCR implementation and pharmacist intervention., (Copyright © 2018 American Society for Microbiology.)

Antibodies have long been recognised as potent vectors for carrying diagnostic medical radionuclides, contrast agents and optical probes to diseased tissue for imaging. The area of ImmunoPET combines the use of positron emission tomography (PET) imaging with antibodies to improve the diagnosis, staging and monitoring of diseases. Recent developments in antibody engineering and PET radiochemistry have led to a new wave of experimental ImmunoPET imaging agents that are based on a range of antibody fragments and affibodies. In contrast to full antibodies, engineered affibody proteins and antibody fragments such as minibodies, diabodies, single-chain variable region fragments (scFvs), and nanobodies are much smaller but retain the essential specificities and affinities of full antibodies in addition to more desirable pharmacokinetics for imaging. Herein, recent key developments in the PET radiolabelling strategies of antibody fragments and related affibody molecules are highlighted, along with the main PET imaging applications of overexpressed antigen-associated tumours and immune cells., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

EMDR therapy is recommended in several guidelines in the International field of psychological trauma. The dual attention stimuli/alternating bilateral stimulation (DAS/ABS) element of EMDR therapy has no proposed mechanism of action agreed upon, which explains the rapid shifts in cognitions and dysfunctional traumatic memory networks that are central to its observable efficacy. This paper discusses an innate, biological mechanism found in biological systems, including the human nervous system that may explain the efficacy of DAS/ABS. This mechanism is stochastic resonance (SR). SR is observed to make unintelligible, subthreshold signals intelligible and facilitates signal transmission. It provides a potential mechanism for discrimination and the selective focusing of attention, which are important factors in effective psychotherapy for the psychologically traumatised individual. The body/mind complex aims to achieve the functional encoding of memories in the neocortex and a key structural crossroads in this process is the thalamus. Activity in the thalamus is decreased in Post-Traumatic Stress Disorder (PTSD) compared to non-PTSD patients and a form of 'gating' is known to occur at the thalamic level. This 'gating' is adaptive and it is postulated to protect the higher neocortical systems in times of trauma. Although the model is initially somewhat counterintuitive, Stochastic Resonance; a form of random 'noise', can be considered 'helpful randomness' and when present in the thalamus SR can help filter and control sensitivity to incoming signals; helping to discriminate what is communicated. Naturally occurring SR is normally present as a result of descending cortico-thalamic activity, but appears attenuated as a result of exposure to trauma. The view of 'noise' in the current era of cell phones and High Definition is generally negative with science going to significant lengths to clean up signals: i.e. removing noise from them. We do not want white noise in our music or during our cell phone calls. However, some researchers invite us to consider that not all noise is bad and the downward cortico-thalamic 'noise' is an example of this category of 'helpful noise'. This paper will discuss the potential role of SR, as the mechanism by which DAS/ABS generates a random (stochastic) signal, facilitating a return to functional memory processing, where there is a lack of naturally occurring noise from the descending cortico-thalamic connections because of exposure to trauma. Modelling the mechanism as SR will facilitate further study into EMDR therapy and this will hopefully encourage perspicacity, where there has previously been derision., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH2PPh2)3, NP3Ph) are reported. Reaction of N-triphos with [MoX3(THF)3] (X = Cl, Br, I) gave the Mo(iii) complex [MoX3(κ2-NP3Ph)(THF)] (1), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N2)(dppm)(κ3-NP3Ph)] (2), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)2(dppm)(κ3-NP3Ph)] (4), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex 2. The reactivity of the dinitrogen complex 2 with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H+, BBr3 and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to 2 resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh2)(PCP)][B(C6F5)4] (7), where PCP, [Ph2PCNHCH2PPh2] is the carbenic ligand formed upon rearrangement from the reaction of 2 with M[B(C6F5)4] (M = Li, Na or K). Single crystal X-ray diffraction of complexes 1, 2, 4 and 7 provided structural confirmation of the N-triphos molybdenum complexes described.

The evolution of cell-adhesion mechanisms in animals facilitated the assembly of organized multicellular tissues. Studies in traditional animal models have revealed two predominant adhesion structures, the adherens junction (AJ) and focal adhesions (FAs), which are involved in the attachment of neighboring cells to each other and to the secreted extracellular matrix (ECM), respectively. The AJ (containing cadherins and catenins) and FAs (comprising integrins, talin, and paxillin) differ in protein composition, but both junctions contain the actin-binding protein vinculin. The near ubiquity of these structures in animals suggests that AJ and FAs evolved early, possibly coincident with multicellularity. However, a challenge to this perspective is that previous studies of sponges-a divergent animal lineage-indicate that their tissues are organized primarily by an alternative, sponge-specific cell-adhesion mechanism called "aggregation factor." In this study, we examined the structure, biochemical properties, and tissue localization of a vinculin ortholog in the sponge Oscarella pearsei ( Op ). Our results indicate that Op vinculin localizes to both cell-cell and cell-ECM contacts and has biochemical and structural properties similar to those of vertebrate vinculin. We propose that Op vinculin played a role in cell adhesion and tissue organization in the last common ancestor of sponges and other animals. These findings provide compelling evidence that sponge tissues are indeed organized like epithelia in other animals and support the notion that AJ- and FA-like structures extend to the earliest periods of animal evolution., (© 2018 by The American Society for Biochemistry and Molecular Biology, Inc.)

Herein we report the preparation of ammonium [ 11 C]thiocyanate via the reaction of [ 11 C]CS 2 with ammonia. The [ 11 C]SCN - ion is demonstrated as a potent nucleophile that can be used to readily generate a range of 11 C-labelled thiocyanate molecules in high conversions. Furthermore, novel 11 C-labelled thiazolone molecules can be easily prepared from the intermediate α-thiocyanatophenones via an acid mediated cyclisation reaction.

Fundamental biological and biomimetic processes, from tissue morphogenesis to soft robotics, rely on the propagation of chemical and mechanical surface waves to signal and coordinate active force generation. The complex interplay between surface geometry and contraction wave dynamics remains poorly understood, but it will be essential for the future design of chemically driven soft robots and active materials. Here, we couple prototypical chemical wave and reaction-diffusion models to non-Euclidean shell mechanics to identify and characterize generic features of chemomechanical wave propagation on active deformable surfaces. Our theoretical framework is validated against recent data from contractile wave measurements on ascidian and starfish oocytes, producing good quantitative agreement in both cases. The theory is then applied to illustrate how geometry and preexisting discrete symmetries can be utilized to focus active elastic surface waves. We highlight the practical potential of chemomechanical coupling by demonstrating spontaneous wave-induced locomotion of elastic shells of various geometries. Altogether, our results show how geometry, elasticity, and chemical signaling can be harnessed to construct dynamically adaptable, autonomously moving mechanical surface waveguides.

Naturally occurring polymers are promising biocompatible materials that have many applications for emerging therapies, drug delivery systems, and diagnostic agents. The handling and processing of such materials still constitutes a major challenge, which can limit the full exploitation of their properties. This study explores an ambient environment processing technique: coaxial electrospray (CO-ES) to encapsulate genistein (an isoflavonoid and model drug), superparamagnetic iron oxide nanoparticles (SPIONs, 10-15 nm), and a fluorophore (BODIPY) into a layered (triglyceride tristearin shell) particulate system, with a view to constructing a theranostic agent. Mode mapping of CO-ES led to an optimized atomization engineering window for stable jetting, leading to encapsulation of SPIONs within particles of diameter 0.65-1.2 μm and drug encapsulation efficiencies of around 92%. Electron microscopy was used to image the encapsulated SPIONs and confirm core-shell triglyceride encapsulation in addition to further physicochemical characterization (AFM, FTIR, DSC, and TGA). Cell viability assays (MTT, HeLa cells) were used to determine optimal SPION loaded particles (∼1 mg/mL), while in vitro release profile experiments (PBS, pH = 7.4) demonstrate a triphasic release profile. Further cell studies confirmed cell uptake and internalization at selected time points (t = 1, 2, and 4 h). The results suggest potential for using the CO-ES technique as an efficient way to encapsulate SPIONs together with sensitive drugs for the development of multimodal particles that have potential application for combined imaging and therapy.

Tissue folding promotes three-dimensional (3D) form during development. In many cases, folding is associated with myosin accumulation at the apical surface of epithelial cells, as seen in the vertebrate neural tube and the Drosophila ventral furrow. This type of folding is characterized by constriction of apical cell surfaces, and the resulting cell shape change is thought to cause tissue folding. Here, we use quantitative microscopy to measure the pattern of transcription, signaling, myosin activation and cell shape in the Drosophila mesoderm. We found that cells within the ventral domain accumulate different amounts of active apical non-muscle myosin 2 depending on the distance from the ventral midline. This gradient in active myosin depends on a newly quantified gradient in upstream signaling proteins. A 3D continuum model of the embryo with induced contractility demonstrates that contractility gradients, but not contractility per se, promote changes to surface curvature and folding. As predicted by the model, experimental broadening of the myosin domain in vivo disrupts tissue curvature where myosin is uniform. Our data argue that apical contractility gradients are important for tissue folding., Competing Interests: Competing interestsThe authors declare no competing or financial interests., (© 2017. Published by The Company of Biologists Ltd.)

Hole quality plays a crucial role in the production of close-tolerance holes utilized in aircraft assembly. Through drilling experiments of carbon fiber-reinforced plastic composites (CFRP), this study investigates the impact of varying drilling feed and speed conditions on fiber pull-out geometries and resulting hole quality parameters. For this study, hole quality parameters include hole size variance, hole roundness, and surface roughness. Fiber pull-out geometries are quantified by using scanning electron microscope (SEM) images of the mechanically-sectioned CFRP-machined holes, to measure pull-out length and depth. Fiber pull-out geometries and the hole quality parameter results are dependent on the drilling feed and spindle speed condition, which determines the forces and undeformed chip thickness during the process. Fiber pull-out geometries influence surface roughness parameters from a surface profilometer, while their effect on other hole quality parameters obtained from a coordinate measuring machine is minimal.

Platform chemicals derived from lignocellulosic plant biomass are viewed as a sustainable replacement for crude oil-based feedstocks. Levulinic acid (LA) is one such biomass-derived chemical that has been widely studied for further catalytic transformation to γ-valerolactone (GVL), an important 'green' fuel additive, solvent, and fine chemical intermediate. Although the transformation of LA to GVL can be achieved using heterogeneous catalysis, homogeneous catalytic systems that operate under milder reactions, give higher selectivities and can be recycled continuously are attracting considerable attention. A range of new homogeneous catalysts have now been demonstrated to efficiently convert LA to GVL and to transform LA directly to other value-added chemicals such as 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF). This Minireview covers recent advances in the area of homogeneous catalysis for the conversion of levulinic acid and levulinic ester derivatives to GVL and chemicals beyond GVL., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The cadherin-catenin complex (CCC) mediates cell-cell adhesion in bilaterian animals by linking extracellular cadherin-based adhesions to the actin cytoskeleton. However, it is unknown whether the basic organization of the complex is conserved across all metazoans. We tested whether protein interactions and actin-binding properties of the CCC are conserved in a nonbilaterian animal, the sea anemone Nematostella vectensis We demonstrated that N. vectensis has a complete repertoire of cadherin-catenin proteins, including two classical cadherins, one α-catenin, and one β-catenin. Using size-exclusion chromatography and multi-angle light scattering, we showed that α-catenin and β-catenin formed a heterodimer that bound N. vectensis Cadherin-1 and -2. Nematostella vectensis α-catenin bound F-actin with equivalent affinity as either a monomer or an α/β-catenin heterodimer, and its affinity for F-actin was, in part, regulated by a novel insert between the N- and C-terminal domains. Nematostella vectensis α-catenin inhibited Arp2/3 complex-mediated nucleation of actin filaments, a regulatory property previously thought to be unique to mammalian αE-catenin. Thus, despite significant differences in sequence, the key interactions of the CCC are conserved between bilaterians and cnidarians, indicating that the core function of the CCC as a link between cell adhesions and the actin cytoskeleton is ancestral in the eumetazoans., (© The Author 2016. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.)