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There is considerable evidence documenting associations between tobacco smoking, including initiation, maintenance, and relapse of addiction, with diminished cardiovascular responses to acute psychological stress. However, less is known about how smokers respond to repeated stress across time. The current study examined patterns of cardiovascular reactivity and adaptation to recurrent stress among 24-h abstinence smokers, smokers who continued to smoke at their normal rate, and non-smokers. Smokers were randomly assigned to one of two groups; ad libitum (n = 42), or 24 h abstinence (n = 61); non-smokers (n = 43) provided comparative referencing. Across the two laboratory sessions, participants (n = 149) were asked to complete a modified version of the trier social stress test, while monitoring systolic and diastolic blood pressure, and heart rate activity. Results showed that while non-smokers had elevated cardiovascular reactivity to begin with, they showed a greater capacity to habituate to recurrent stress across sessions. The data also suggest that smokers displayed lower cardiovascular reactivity to acute psychological stress and showed little habituation to repeated stress. In adjusted models, smokers exhibited less systolic blood pressure habituation to stress. This response profile in smokers may be a potential mechanism that leads to further cardiotoxic effects on health., (© 2024 The Author(s). Psychophysiology published by Wiley Periodicals LLC on behalf of Society for Psychophysiological Research.)

The instrumental variable method is widely used in causal inference research to improve the accuracy of estimating causal effects. However, the weak correlation between instruments and exposure, as well as the direct impact of instruments on the outcome, can lead to biased estimates. To mitigate the bias introduced by such instruments in nonlinear causal inference, we propose a two-stage nonlinear causal effect estimation based on model averaging. The model uses different subsets of instruments in the first stage to predict exposure after a nonlinear transformation with the help of sliced inverse regression. In the second stage, adaptive Lasso penalty is applied to instruments to obtain the estimation of causal effect. We prove that the proposed estimator exhibits favorable asymptotic properties and evaluate its performance through a series of numerical studies, demonstrating its effectiveness in identifying nonlinear causal effects and its capability to handle scenarios with weak and invalid instruments. We apply the proposed method to the Atherosclerosis Risk in Communities dataset to investigate the relationship between BMI and hypertension., (© 2024 John Wiley & Sons Ltd.)

Accelerated failure time models are appealing due to their intuitive interpretation. However, when covariates are subject to measurement errors, naive estimation becomes severely biased. To address this issue, the regression calibration (RC) approach is a widely applicable and effective method. Traditionally, the RC method requires a good predictor for the true covariate, which can be obtained through parametric distribution assumptions or validation datasets. Consequently, the performance of the estimator depends on the plausibility of these assumptions. In this work, we propose a novel method that utilizes error augmentation to duplicate covariates, facilitating nonparametric estimation. Our approach does not require a validation set or parametric distribution assumptions for the true covariate. Through simulation studies, we demonstrate that our approach is more robust and less impacted by heavy censoring rates compared to conventional analyses. Additionally, an analysis of a subset of a real dataset suggests that the conventional RC method may have a tendency to overcorrect the attenuation effect of measurement error., (© 2024 John Wiley & Sons Ltd.)

Symbiotic nitrogen fixation (SNF) provides nitrogen for soybean. A primary challenge in enhancing yield through efficient SNF lies in striking a balance between its high energy consumption and plant growth. However, the systemic transcriptional reprogramming during nodulation remains limited. Here, this work conducts a comprehensive RNA-seq of the roots, cotyledons and leaves of inoculated-soybean. This work finds 88,814 mRNAs and 6,156 noncoding RNAs (ncRNAs) across various organs. Notably, this work identifies 6,679 nodulation-regulated mRNAs (NR-mRNAs), 1,681 long noncoding RNAs (lncRNAs) (NR-lncRNAs), and 59 miRNAs (NR-miRNAs). The majority of these NR-RNAs are associated with plant-microbial interaction and exhibit high organ specificity. Roots display the highest abundance of NR-ncRNAs and the most dynamic crosstalk between NR-lncRNAs and NR-miRNAs in a GmNARK-dependent manner. This indicates that while each tissue responds uniquely, GmNARK serves as a primary regulator of the transcriptional control of nodulated-plants. Furthermore, this work proves that lnc-NNR6788 and lnc-NNR7059 promote nodulation by regulating their target genes. This work also shows that the nodulation- and GmNARK-regulated (NNR) lnc-NNR4481 negatively regulates nodulation through miR172c within a competing endogenous RNA (ceRNA) network. The spatial organ-type transcriptomic atlas establishes a benchmark and provides a valuable resource for integrative analyses of the mechanism underlying of nodulation and plant growth balance., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Clustering analysis of functional data, which comprises observations that evolve continuously over time or space, has gained increasing attention across various scientific disciplines. Practical applications often involve functional data that are contaminated with measurement errors arising from imprecise instruments, sampling errors, or other sources. These errors can significantly distort the inherent data structure, resulting in erroneous clustering outcomes. In this article, we propose a simulation-based approach designed to mitigate the impact of measurement errors. Our proposed method estimates the distribution of functional measurement errors through repeated measurements. Subsequently, the clustering algorithm is applied to simulated data generated from the conditional distribution of the unobserved true functional data given the observed contaminated functional data, accounting for the adjustments made to rectify measurement errors. We illustrate through simulations show that the proposed method has improved numerical performance than the naive methods that neglect such errors. Our proposed method was applied to a childhood obesity study, giving more reliable clustering results., (© 2024 John Wiley & Sons Ltd.)

Training one limb with a high-load has been shown to augment strength changes in the opposite limb training with a low-load (via cross-education of strength), indicating that within-subject models can be problematic when investigating strength changes. This study examined if the cross-education of strength from unilateral high-load training could augment the strength changes in the opposite arm undergoing the same unilateral high-load training. 160 participants were randomized to one of four groups: (1) training on the dominant arm followed by the non-dominant arm (D + ND), (2) training on the dominant arm only (D-Only), (3) training on the non-dominant arm only (ND-Only), and (4) a non-exercise control. All exercise groups performed 18 sessions of unilateral high-load elbow flexion exercise over 6 weeks. Participants were compared for changes in 1RM strength and muscle thickness. Changes in strength of the non-dominant arm were greater in D + ND (2.7 kg) and ND-Only (2.6 kg) compared to D-Only (1.5 kg) and control (-0.2 kg), while the changes were greater in D-Only compared to control. The same finding was observed in the dominant arm. Only the arms being directly trained observed increases in muscle thickness. Unilateral high-load resistance training increased strength in the opposite untrained arm, without changes in muscle thickness. This cross-education of strength did not augment the strength changes in the contralateral arm undergoing the same unilateral high-load training. However, it does not necessarily indicate that within-subject models are methodologically sound to investigate strength change if both limbs are trained with a high-load., (© 2024 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

The plant defense against insects is multiple layers of interactions. They defend through direct defense and indirect defense. Direct defenses include both physical and chemical barriers that hinder insect growth, development, and reproduction. In contrast, indirect defenses do not affect insects directly but instead suppress them by releasing volatile compounds that attract the natural enemies of herbivores. Insects overcome plant defenses by deactivating biochemical defenses, suppressing defense signaling through effectors, and altering their behavior through chemical regulation. There is always a genetic war between plants and insects. In this genetic war, plant-insect co-evolution act as both weapons and messengers. Because plants always look for new strategies to avoid insects by developing adaptation. There are molecular processes that regulate the interaction between plants and insect. Here, we examine the genes and proteins involved in plant-insect interactions and explore how their discovery has shaped the current model of the plant genome's role. Plants detect damage-associated and herbivore-associated molecular patterns through receptors, which trigger early signaling pathways involving Ca 2+ , reactive oxygen species, and MAP kinases. The specific defense mechanisms are activated through gene signaling pathways, including phytohormones, secondary metabolites, and transcription factors. Expanding plant genome approaches to unexplored dimensions in fending off insects should be a future priority in order to develop management strategies., (© 2024 Wiley Periodicals LLC.)

Permanent magnets (PMs) containing rare earth elements (REEs) can generate energy in a sustainable manner. With an anticipated tenfold increase in REEs demand by 2050, one of the crucial strategies to meet the demand is developing of efficient recycling methods. NdFeB PMs are the most widely employed, however, the similar chemical properties of Nd (20-30 % wt.) and Dy (0-10 % wt.) make their recycling challenging, but possible using appropriate ligands. In this work, we investigated commercially available 8-hydroxyquinolines (HQs) as potential Fe/Nd/Dy complexing agents enabling metal separation by selective precipitation playing on specific structure/property (solubility) relationship. Specifically, test ethanolic solutions of nitrate salts, prepared to mimic the main components of a PM leachate, were treated with functionalized HQs. We demonstrated that Fe 3+ can be separated as insoluble [Fe(Q Cl,I ) 3 ] from soluble [REE(Q Cl,I ) 4 ] - complexes (Q Cl,I - : 5-Cl-7-I-8-hydoxyquinolinate). Following that, Q Cl - (5-Cl-8-hydroxyquinolinate) formed insoluble [Nd 3 (Q Cl ) 9 ] and soluble (Bu 4 N)[Dy(Q Cl ) 4 ]. The process ultimately gave a solution phase containing Dy with only traces of Nd. In a preliminary attempt to assess the potentiality of a low environmental impact process, REEs were recovered as oxalates, while the ligands as well as Bu 4 N + ions, were regenerated and internally reused, thus contributing to the sustainability of a possible metal recovery process., (© 2024 Wiley-VCH GmbH.)

The main objective of this rapid systematic review was to examine how the COVID-19 pandemic impacted peer relationships for adolescents (10-25 years of age) around the globe. We focused on four indices of peer relationships: (1) loneliness, (2) social connectedness, (3) social support, and (4) social media use. In addition, we examined gender and age differences. Four databases (APA PsychInfo, PubMed, Scopus, and Web of Science) were searched for articles published from January 2020 to November 2022. A total of 96 studies (cross-sectional: n = 66, longitudinal: n = 30, quantitative: n = 67, qualitative: n = 12, mixed-methods: n = 17) met our inclusion criteria (empirical observational studies with data on at least one of the indices of interest, cross-sectional data on COVID-19-related experiences or longitudinal data collected during the pandemic, age range of 10-25 years, typically developing adolescents). We extracted data and conducted a narrative synthesis. Findings suggest that COVID-19 disruptions negatively impacted peer relationships for youth. Most studies reported either an increase in loneliness over the course of the pandemic or a positive association between loneliness and COVID-19-related experiences. Similar findings were observed for increased social media use as a means of continued communication and connection. Fewer studies focused on social support but those that did reported a decrease or negative association with COVID-19-related experiences. Lastly, findings suggest a mixed impact on social connectedness, which might be due to the strengthening of closer ties and weakening of more distant relationships. Results for gender differences were mixed, and a systematic comparison of differences across ages was not possible. The heterogeneity in measures of COVID-19-related experiences as well as timing of data collection prevented a more nuanced examination of short and more long-term impacts., (© 2024 Society for Research on Adolescence.)

The rare earth elements (REEs) are critical resources for many clean energy technologies, but are difficult to obtain in their elementally pure forms because of their nearly identical chemical properties. Here, an analogue of macropa, G-macropa, was synthesized and employed for an aqueous precipitation-based separation of Nd 3+ and Dy 3+ . G-macropa maintains the same thermodynamic preference for the large REEs as macropa, but shows smaller thermodynamic stability constants. Molecular dynamics studies demonstrate that the binding affinity differences of these chelators for Nd 3+ and Dy 3+ is a consequence of the presence or absence of an inner-sphere water molecule, which alters the donor strength of the macrocyclic ethers. Leveraging the small REE affinity of G-macropa, we demonstrate that within aqueous solutions of Nd 3+ , Dy 3+ , and G-macropa, the addition of HCO 3 - selectively precipitates Dy 2 (CO 3 ) 3 , leaving the Nd 3+ -G-macropa complex in solution. With this method, remarkably high separation factors of 841 and 741 are achieved for 50 : 50 and 75 : 25 mixtures. Further studies involving Nd 3+ :Dy 3+ ratios of 95 : 5 in authentic magnet waste also afford an efficient separation as well. Lastly, G-macropa is recovered via crystallization with HCl and used for subsequent extractions, demonstrating its good recyclability., (© 2024 Wiley-VCH GmbH.)

In this work, we used photoinert anhydrous cerium(III) chloride, to form a transient charge-transfer (CT) complex with NXS (N-bromosuccinimide or NBS and N-iodosuccinimide or NIS) in acetonitrile. These transient CT complexes acted as a semi-heterogeneous photocatalyst. These complexes allowed the Ce(III) ions to absorb light, turning them into strong electron donors that transferred electrons to NXS. This created halide radicals from NXS radical anions, helping to turn N-propargylamides into oxazole aldehydes. Experiments with DMPO and spin-trapping showed that a radical-based mechanism followed a single electron transfer (SET) pathway. Notably, CeCl 3 was reused after the reaction without much decomposition, as it was regenerated and separated through simple filtration., (© 2024 Wiley-VCH GmbH.)

To evaluate bifunctional ligand reactivity involving NH acidic sites in the secondary coordination sphere, complexes where the proton has been substituted with a methyl group (NMe) are often investigated. An alternative strategy involves substitution of the NH group for an O. This contribution considers and compares the merits of these approaches; the synthesis and characterization of cationic square-planar Rh carbonyl complexes bearing diprotic bispyrazole pyridine ligand L1, and the bis-methylated pyrazole pyridine ligand L1Me are described. The syntheses and characterization of the novel monoprotic pyrazole isoxazole pyridine ligand L2 and aprotic bisisoxazole pyridine ligand L3, and their corresponding Rh carbonyl complexes are also described. Comparison of the CO stretching frequencies of the four Rh complexes suggest that substitutions of NH with NMe, as well as with O, lead to significant electronic differences. These electronic differences result in different reactivities with respect to ligand addition/substitution of the Rh carbonyl complexes. Overall, the data suggest that electronic differences arising due to the NH substitutions can be significant and should be considered when the NH group is substituted in investigations of the participation of the NH proton in a reaction., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Epithelial cysts and organoids are multicellular hollow structures formed by correctly polarized epithelial cells. Important in steering these cysts from single cells is the dynamic regulation of extracellular matrix presented ligands, and matrix dynamics. Here, control over the effective ligand concentration is introduced, decoupled from bulk and local mechanical properties, in synthetic dynamic supramolecular hydrogels formed through noncovalent crosslinking of supramolecular fibers. Control over the effective ligand concentration is realized by 1) keeping the ligand concentration constant, but changing the concentration of nonfunctionalized molecules or by 2) varying the ligand concentration, while keeping the concentration of non-functionalized molecules constant. The results show that in 2D, the effective ligand concentration within the supramolecular fibers rather than gel stiffness (from 0.1 to 8 kPa) regulates epithelial polarity. In 3D, increasing the effective ligand concentration from 0.5 × 10 -3 to 2 × 10 -3 m strengthens the effect of increased gel stiffness from 0.1 to 2 kPa, to synergistically yield more correctly polarized cysts. Through integrin manipulation, it is shown that epithelial polarity is regulated by tension-based homeostasis between cells and matrix. The results reveal the effective ligand concentration as influential factor in regulating epithelial polarity and provide insights on engineering of synthetic biomaterials for cell and organoid culture., (© 2023 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Contingency management (CM), which involves the delivery of incentives upon meeting behavioral goals, has the potential to improve substance use treatment outcomes. The intervention allows for flexibility through numerous modifiable components including changes to incentive magnitude and schedule, target behavior, and intervention structure. Unfortunately, numerous changes in the substance use landscape have occurred in the past 10 to 15 years: Substances are more potent, overdose risk has increased, new substances and methods of use have been introduced, and substance classes are increasingly being intentionally and unintentionally mixed. These developments potentially undermine CM outcomes. We explored recent substance use changes due to legislative, regulatory, social, and economic factors for four substance classes: stimulants, opioids, tobacco, and cannabis. We discuss potential adjustments to the modifiable components of CM for future research in response to these changes. By continually adapting to the shifting substance use landscape, CM can maintain optimal efficacy., (© 2024 The Author(s). Journal of Applied Behavior Analysis published by Wiley Periodicals LLC on behalf of Society for the Experimental Analysis of Behavior (SEAB).)

Unsymmetric boron (III) subphthalocyanines with a triselenole ring or a diselenete ring and eight fluoro groups were prepared by the reaction of 5,6-dicyano-4,7-diethylbenzo-[1,2,3]triselenole and tetrafluorophthalonitrile with trichloroborane in xylene. The reaction was accompanied by a contraction of the triselenole ring to the diselenete ring. The substrate, dicyanobenzo[1,2,3]triselenole, was prepared by a new procedure via a photolytic demethylenation reaction of 3,7-diethyl[1,3]diselenolophthalonitrile using a 10 W white LED light. While triselenolosubphthalocyanine was treated by triphenylphosphine to give the diselenete derivative, the reaction of diselenetosubphthalocyanine with Woolion's reagent produced the expanded triselenole ring. The diselenete derivative reacted with tetrakis(triphenylphosphine)platinum to yield the corresponding platinum complex with Se-Pt bonds. Q-band absorption for the products appeared at around λ max =590 nm in the UV-vis spectrum and weak emission was observed at about λ e =620 nm. When diselenetosubphthalocyanine was treated with pentachloro antimonate in dichloromethane or sodium metal in hexane/tetrahydrofuran, the solution showed strong ESR signals. The structures of model compounds were optimized using the DFT method with the Gaussian 09 program at the B3LYP/6-31G (d, p) level., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Drug overdose is a leading cause of death among adults in the United States, prompting calls for more surveillance data and data sharing across public health and law enforcement to address the crisis. This paper integrates Black feminist science and technology studies (STS) into an anthropological analysis of the collision of public health, policing, and technology as embedded in the US National Overdose Response Strategy and its technological innovation, the Overdose Detection Mapping Application Program (ODMAP). The dystopian Netflix series "Black Mirror," which explores the seemingly useful but quietly destructive potential of technology, offers a lens through which to speculate upon and anticipate the harms of collaborative surveillance projects. Ultimately, I ask: are such technological interventions a benevolent approach to a public health crisis or are we looking into a black mirror of racialized surveillance and criminalization of overdose in the United States?, (© 2024 The Author(s). Medical Anthropology Quarterly published by Wiley Periodicals LLC on behalf of American Anthropological Association.)

The nitrido-ate complex [(PN) 2 Ti(N){μ 2 -K(OEt 2 )}] 2 (1) (PN - =(N-(2-P i Pr 2 -4-methylphenyl)-2,4,6-Me 3 C 6 H 2 ) reductively couples CO and isocyanides in the presence of DME or cryptand (Kryptofix222), to form rare, five-coordinate Ti II complexes having a linear cumulene motif, [K(L)][(PN) 2 Ti(NCE)] (E=O, L=Kryptofix222, (2); E=NAd, L=3 DME, (3); E=N t Bu, L=3 DME, (4); E=NAd, L=Kryptofix222, (5)). Oxidation of 2-5 with [Fc][OTf] afforded an isostructural Ti III center containing a neutral cumulene, [(PN) 2 Ti(NCE)] (E=O, (6); E=NAd (7), N t Bu (8)) and characterization by CW X-band EPR spectroscopy, revealed unpaired electron to be metal centric. Moreover, 1e - reduction of 6 and 7 in the presence of Kryptofix222cleanly reformed corresponding discrete Ti II complexes 2 and 5, which were further characterized by solution magnetization measurements and high-frequency and -field EPR (HFEPR) spectroscopy. Furthermore, oxidation of 7 with [Fc*][B(C 6 F 5 ) 4 ] resulted in a ligand disproportionated Ti IV complex having transoid carbodiimides, [(PN) 2 Ti(NCNAd) 2 ] (9). Comparison of spectroscopic, structural, and computational data for the divalent, trivalent, and tetravalent systems, including their 15 N enriched isotopomers demonstrate these cumulenes to decrease in order of backbonding as Ti II →Ti III →Ti IV and increasing order of π-donation as Ti II →Ti III →Ti IV , thus displaying more covalency in Ti III species. Lastly, we show a synthetic cycle whereby complex 1 can deliver an N-atom to CO and CNAd., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Compared to 3D perovskites, 2D perovskites exhibit excellent stability, structural diversity, and tunable bandgaps, making them highly promising for applications in solar cells, light-emitting diodes, and photodetectors. However, the trade-off for worse charge transport is a critical issue that needs to be addressed. This comprehensive review first discusses the structure of 3D and 2D metal halide perovskites, then summarizes the significant factors influencing charge transport in detail and provides a brief overview of the testing methods. Subsequently, various strategies to improve the charge transport are presented, including tuning A'-site organic spacer cations, A-site cations, B-site metal cations, and X-site halide ions. Finally, an outlook on the future development of improving the 2D perovskites' charge transport is discussed., (© 2024 Wiley‐VCH GmbH.)

Pulmonary hypoplasia, Diaphragmatic anomalies, Anophthalmia/microphthalmia, and Cardiac defects (PDAC) syndrome is a genetically heterogeneous multiple congenital malformation syndrome. Although pathogenic variants in RARB and STRA6 are established causes of PDAC, many PDAC cases remain unsolved at the molecular level. Recently, we proposed biallelic WNT7B variants as a novel etiology based on several families with typical features of PDAC syndrome albeit with variable expressivity. Here, we report three patients from two families that share a novel founder variant in WNT7B (c.739C > T; Arg247Trp). The phenotypic expression of this variant ranges from typical PDAC features to isolated genitourinary anomalies. Similar to previously reported PDAC-associated WNT7B variants, this variant was found to significantly impair WNT7B signaling activity further corroborating its proposed pathogenicity. This report adds further evidence to WNT7B-related PDAC and expands its variable expressivity., (© 2024 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

2D perovskites have received great attention recently due to their structural tunability and environmental stability, making them highly promising candidates for various applications by breaking property bottlenecks that affect established materials. However, in 2D perovskites, the complicated interplay between organic spacers and inorganic slabs makes structural analysis challenging to interpret. A deeper understanding of the structure-property relationship in these systems is urgently needed to enable high-performance tunable optoelectronic devices. Herein, this study examines how structural changes, from constant lattice distortion and variable structural evolution, modeled with both static and dynamic structural descriptors, affect macroscopic properties and ultimately device performance. The effect of chemical composition, crystallographic inhomogeneity, and mechanical-stress-induced static structural changes and corresponding electronic band variations is reported. In addition, the structure dynamics are described from the viewpoint of anharmonic vibrations, which impact electron-phonon coupling and the carriers' dynamic processes. Correlated carrier-matter interactions, known as polarons and acting on fine electronic structures, are then discussed. Finally, reliable guidelines to facilitate design to exploit structural features and rationally achieve breakthroughs in 2D perovskite applications are proposed. This review provides a global structural landscape of 2D perovskites, expected to promote the prosperity of these materials in emerging device applications., (© 2024 Wiley‐VCH GmbH.)

The synthesis of group 4 metal 1-metallacyclobuta-2,3-dienes as organometallic analogues of elusive 1,2-cyclobutadiene has so far been limited to SiMe 3 substituted examples. We present the synthesis of two Ph substituted dilithiated ligand precursors for the preparation of four new 1-metallacyclobuta-2,3-dienes [rac-(ebthi)M] (M=Ti, Zr; ebthi=1,2-ethylene-1,10-bis(η 5 -tetrahydroindenyl)). The organolithium compounds [Li 2 (RC 3 Ph)] (1 b: R=Ph, 1 c: R=SiMe 3 ) as well as the metallacycles of the general formula [rac-(ebthi)M(R 1 C 3 R 2 )] (2 b: M=Ti, R 1 =R 2 =Ph, 2 c: M=Ti, R 1 =Ph, R 2 =SiMe 3 ; 3 b: M=Zr, R 1 =R 2 =Ph; 3 c: M=Zr, R 1 =Ph, R 2 =SiMe 3 ) were fully characterised. Single crystal X-ray diffraction and quantum chemical bond analysis of the Ti and Zr complexes reveal ligand influence on the biradicaloid character of the titanocene complexes. X-band EPR spectroscopy of structurally similar Ti complexes [rac-(ebthi)Ti(Me 3 SiC 3 SiMe 3 )] (2 a), 2 b, and 2 c was carried out to evaluate the accessibility of an EPR active triplet state. Cyclic voltammetry shows that introduction of Ph groups renders the complexes easier to reduce. 13 C CPMAS NMR analysis provides insights into the cause of the low field shift of the resonances of metal-bonded carbon atoms and provides evidence of the absence of the β-C-Ti interaction., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

We introduce the heterocumulene ligand [(Ad)NCC( t Bu)] - (Ad=1-adamantyl (C 10 H 15 ), t Bu=tert-butyl, (C 4 H 9 )), which can adopt two forms, the azaalleneyl and ynamide. This ligand platform can undergo a reversible chelotropic shift using Brønsted acid-base chemistry, which promotes an unprecedented spin-state change of the [V III ] ion. These unique scaffolds are prepared via addition of 1-adamantyl isonitrile (C≡NAd) across the alkylidyne in complexes [(BDI)V≡C t Bu(OTf)] (A) (BDI - =ArNC(CH 3 )CHC(CH 3 )NAr), Ar=2,6- i Pr 2 C 6 H 3 ) and [(dBDI)V≡C t Bu(OEt 2 )] (B) (dBDI 2- =ArNC(CH 3 )CHC(CH 2 )NAr). Complex A reacts with C≡NAd, to generate the high-spin [V III ] complex with a κ 1 -N-ynamide ligand, [(BDI)V{κ 1 -N-(Ad)NCC( t Bu)}(OTf)] (1). Conversely, B reacts with C≡NAd to generate a low-spin [V III ] diamagnetic complex having a chelated κ 2 -C,N-azaalleneyl ligand, [(dBDI)V{κ 2 -N,C-(Ad)NCC( t Bu)}] (2). Theoretical studies have been applied to better understand the mechanism of formation of 2 and the electronic reconfiguration upon structural rearrangement by the alteration of ligand denticity between 1 and 2., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The need for synthetic methodologies capable of rapidly altering molecular structure are in high demand. Most existing methods to modify scaffolds rely on net exothermicity to drive the desired transformation. We sought to develop a general strategy for the cleavage of C-C bonds β to hydroxyl groups independent of inherent substrate strain. To this end we have applied a multicatalytic cerium photoredox-based system capable of activating O-H bonds in lactols to deliver formate esters. The same system is also capable of effecting hydrodecarboxylation and hydrodecarbonylation reactions. Initial mechanistic probes demonstrate atomic chlorine (Cl⋅) is generated under the reaction conditions, but substrate activation through cerium-alkoxides or -carboxylates cannot be ruled out., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Reaction of [CuH(PPh 3 )] 6 with 1 equiv. of Tl(OTf) results in formation of [Cu 6 TlH 6 (PPh 3 ) 6 ][OTf] ([1]OTf]), which can be isolated in good yields. Variable-temperature 1 H NMR spectroscopy, in combination with density functional theory (DFT) calculations, confirms the presence of a rare Tl-H orbital interaction. According to DFT, the 1 H chemical shift of the Tl-adjacent hydride ligands of [1] + includes 7.7 ppm of deshielding due to spin-orbit effects from the heavy Tl atom. This study provides valuable new insights into a rare class of metal hydrides, given that [1][OTf] is only the third isolable species reported to contain a Tl-H interaction., (© 2024 Wiley-VCH GmbH.)

Mountain pine beetles (MPBs) pose a substantial threat to North American pine forests, causing extensive tree mortality over large areas. Their tree-killing ability is closely linked to mass aggregation on host trees triggered via pheromones and dependence on their symbiotic fungi. However, the influence of a changing climate on the biology of MPBs and their co-evolved interactions with their fungal symbionts remains uncertain. To investigate this, male and female pairs of beetles were introduced into freshly cut logs from lodgepole pine trees and placed in controlled climate chambers with manipulated environmental conditions, including two levels of CO 2 (ambient vs. 1000 ppm), O 3 (ambient vs. 100 ppb) and humidity (33% vs. 65%). The beetle-infested logs were left in these chambers for 1 month and then returned to ambient conditions until brood emergence. Emerging broods were collected for further analysis. Additionally, three species of fungal symbionts (Grosmannia clavigera, Ophiostoma montium and Leptographium longiclavatum) were subjected to the same CO 2 , O 3 and humidity conditions for 5 days. Lower humidity promoted MPB reproduction and fungal growth. Elevated CO 2 accelerated larval growth and emergence while improving brood pheromone production. Elevated O 3 had a negative impact on MPB reproduction and brood fitness while improving its immune responses to an entomopathogenic fungus (Beauveria bassiana). It also inhibited fungal growth and reproduction, whereas elevated CO 2 had varied (positive or negative) effects on fungal growth and ergosterol (proxy to fungal mass) production depending on the fungal species. Together, these findings suggest that climate change can potentially alter the interactions between MPBs and their fungal symbionts, highlighting the importance of understanding how climate change affects forest pests and their symbiotic relationships to develop effective management strategies in the future., (© 2024 The Authors. Global Change Biology published by John Wiley & Sons Ltd.)

There is scarce empirical evidence examining whether sexual initiation and power are associated with each other. Utilizing latent profile analyses, we examined in a nationally representative sample of US newlywed heterosexual couples (N = 1,948 couples) whether wives' and husbands' sexual initiation patterns and satisfaction with these patterns were associated with membership in different profiles of wives' and husbands' perceptions of shared relational power while accounting for both partner's satisfaction with sexual frequency. We found four profiles of wives' and husbands' perceptions of power. The most common profile was when both wives and husbands perceived high levels of power compared to other profiles, but wives had significantly higher reports of perceived power than husbands (High Power, Wife Higher; 40.8%). Husbands' sexual initiation patterns were not associated with profile membership. Wives who reported equal sexual initiation patterns had a higher probability of being in the High Power, Wife Higher profile compared to the Wife Low Power, Husband Moderate Power profile. Both wives' and husbands' satisfaction with sexual initiation patterns were associated with profile membership. Wives and husbands that were satisfied with sexual initiation patterns had a higher probability of being in the High Power, Wife Higher profile compared to the profile where both wives and husbands had high perceptions of shared relational power compared to other profiles, but their scores were not significantly different from each other (High Power, Equal)., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Objective: To assess the risk of aspiration associated with post-swallow residue subsites in Fiberoptic Endoscopic Evaluation of Swallowing (FEES) in bottle-fed infants <1 year of age., Methods: This is a retrospective matched-pairs cohort study at an academic tertiary children's hospital. FEES and Videofluoroscopic Swallowing Study (VFSS) trials performed within the same infant <5 days apart were paired by matching bolus consistency and bottle flow rate. Positive aspiration was defined by the "or rule" in which aspiration is positive when either FEES or VFSS within a matched pair is positive., Results: Eighty-seven FEES-VFSS matched pairs from 29 patients (16 males; mean [SD] age, 2.9 [2.8] months) were included. The rate of positive aspiration, as defined by the "or rule", was 59% (51/87). In FEES, post-swallow pyriform sinus residue was present in 16% (14/87) and anterior commissure residue 27% (31/87). Risk of positive aspiration was increased by pyriform sinus residue (odds ratio [OR] 5.4, 95% confidence interval [CI] 1.9-19.3, p < 0.01) and anterior commissure residue in FEES (OR 2.5, 95% CI 1.1-6.1, p = 0.03). In the neonate subgroup, <1 month of age, multivariate-adjusted analysis showed that anterior commissure residue had better diagnostic accuracy for aspiration than in older infants (overall 70% vs. 42%, p < 0.01; sensitivity 60% vs. 10%, p < 0.01), whereas pyriform sinus residue had worse accuracy (overall 41% vs. 70%, p = 0.02; sensitivity 13% vs. 43%, p = 0.02)., Conclusion: This study demonstrates that pyriform sinus and anterior commissure residue during infant FEES were associated with fivefold and twofold increased risk of aspiration, respectively., Level of Evidence: 3: Using a retrospective matched-pairs cohort, this study assesses the diagnostic accuracy of post-swallow residue in FEES for predicting aspiration. Laryngoscope, 134:1431-1436, 2024., (© 2023 The American Laryngological, Rhinological and Otological Society, Inc.)

Chiral molecular switches are attracting attention as they could pave the way to chiral molecular machines. Herein, we report on the design and synthesis of a single molecule chiral switch based on a cyclotriveratrylene scaffold, in which the chirality inversion is controlled by the solvent. Hemicryptophanes are built around a C 3 cyclotriveratrylene chiral unit, with either M or P handedness, connected to another tripod and usually displaying an "out" configuration. Here, we demonstrate that solvents are able to control the "in" and "out" configurations of the CTV unit, creating a chiral molecular switch from (M/P)"in" to (P/M)"out" handedness. The full characterization of the "in" and "out" configurations and of the chirality switch were made possible by combining NMR, HPLC, ECD, DFT and molecular dynamics. Interestingly, bulky aromatic solvents such as 2-t-butylphenol favor the "in" configuration while polar aprotic solvents such as acetone favor the "out" configuration. This chiral switch was found to be fully reversible allowing the system to oscillate between two different M and P configurations several times upon the action of solvents stimuli., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

This study seeks to build on previous research about how pornography use is associated with relationship outcomes. Using the 3AM model (Wright, 2011) as a theoretical guide, sexual behaviors were tested as a possible mediator of the association between pornography use and relationship well-being. Using a national data set of individuals in heterosexual relationships (n = 2519), associations between different types of pornography use (alone use vs. joint use), sexual behaviors, and relationship outcomes were analyzed. Results showed that pornography use with a partner is a distinct activity when compared to pornography use alone. Additionally, significant indirect relationships between pornography use and relationship outcomes were found through sexual behaviors. Both vaginal sex and oral sex had positive effects, while anal sex had a unique, negative effect (use of sex toys was not significantly related). Future research should continue to examine the context of pornography use and how it is related to behaviors and outcomes in relationships., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Catalytic C-N bond formation by direct activation of C-H bonds offers wide synthetic potential. En route to C-H amination, complexes with organic azides are critical precursors towards the reactive nitrene intermediate. Despite their relevance, α-N coordinated organoazide complexes are scarce in general, and elusive with iron, although iron complexes are by far the most active catalysts for C-H amination with organoazides. Herein, we report the synthesis of a stable iron α-N coordinated organoazide complex from [Fe(N(SiMe 3 ) 2 ) 2 ] and AdN 3 (Ad=1-adamantyl) and its crystallographic, IR, NMR and zero-field 57 Fe Mössbauer spectroscopic characterization. These analyses revealed that the organoazide is in fast equilibrium between the free and coordinated state (K eq =62). Photo-crystallography experiments showed gradual dissociation of N 2 , which imparted an Fe-N bond shortening and correspond to structural snapshots of the formation of an iron imido/nitrene complex. Reactivity of the organoazide complex in solution showed complete loss of N 2 , and subsequent formation of a C-H aminated product via nitrene insertion into a C-H bond of the N(SiMe 3 ) 2 ligand. Monitoring this reaction by 1 H NMR spectroscopy indicates the transient formation of the imido/nitrene intermediate, which was supported by Mössbauer spectroscopy in frozen solution., (© 2023 Wiley-VCH GmbH.)

Transition metal triple-decker complexes are an interesting class of sandwich complexes that engrossed great attention due to their structures and properties. Over the decades, synthesis of triple-decker complexes featuring homocyclic, heterocyclic or π-conjugated rings as middle decks have been abundantly reported. In this regard, the chemistry of such complexes bearing boron in the middle deck are well explored due to the ability of boron-containing cycles to readily coordinate bifacially with metal atoms thereby forming triple-decker complexes. On the other hand, electron counting rules and theoretical calculations have strengthened our knowledge of the structure and bonding in these complexes. Further, these complexes can be used as synthons to generate organometallic polymers having interesting electronic, optical and magnetic properties that can be appropriately tuned to cater to a wide range of applications. In our quest for novel metallaboranes and metallaheteroboranes, we have been successful in isolating various triple-decker complexes that feature boron in the middle deck. This review explained elaborately the synthesis, structures, and bonding in such complexes reported by us and others., (© 2023 Wiley-VCH GmbH.)

Oncolytic Viruses (OVs) have emerged as a promising treatment option for cancer thanks to their significant research potential and encouraging results. These viruses exert a profound impact on the tumor microenvironment, making them effective against various types of cancer. In contrast, the efficacy of Chimeric antigen receptor (CAR)-T cell therapy in treating solid tumors is relatively low. The combination of OVs and CAR-T cell therapy, however, is a promising area of research. OVs play a crucial role in enhancing the tumor-suppressive microenvironment, which in turn enables CAR-T cells to function efficiently in the context of solid malignancies. This review aims to provide a comprehensive analysis of the benefits and drawbacks of OV therapy and CAR-T cell therapy, with a focus on the potential of combining these two treatment approaches., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Although the smallpox virus has been eradicated worldwide, the World Health Organization (WHO) has issued a warning about the virus's potential to propagate globally. The WHO labeled monkeypox a world public health emergency in July 2022, requiring urgent prevention and treatment. The monkeypox virus is a part of the Poxviridae family, Orthopoxvirus genus, and is accountable for smallpox, which has killed over a million people in the past. Natural hosts of the virus include squirrels, Gambian rodents, chimpanzees, and other monkeys. The monkeypox virus has transmitted to humans through primary vectors (various animal species) and secondary vectors, including direct touch with lesions, breathing particles from body fluids, and infected bedding. The viral particles are ovoid or brick-shaped, 200-250 nm in diameter, contain a single double-stranded DNA molecule, and reproduce only in the cytoplasm of infected cells. Monkeypox causes fever, cold, muscle pains, headache, fatigue, and backache. The phylogenetic investigation distinguished between two genetic clades of monkeypox: the more pathogenic Congo Basin clade and the West Africa clade. In recent years, the geographical spread of the human monkeypox virus has accelerated despite a paucity of information regarding the disease's emergence, ecology, and epidemiology. Using lesion samples and polymerase chain reaction (PCR), the monkeypox virus was diagnosed. In the USA, the improved Ankara vaccine can now be used to protect people who are at a higher risk of getting monkeypox. Antivirals that we have now work well against smallpox and may stop the spread of monkeypox, but there is no particular therapy for monkeypox., (© 2024. The Author(s), under exclusive license to Springer Nature Switzerland AG.)

Here we report the use of a base metal complex [( tBu pyrpyrr 2 )Fe(OEt 2 )] (1-OEt 2 ) ( tBu pyrpyrr 2 2- =3,5-tBu 2 -bis(pyrrolyl)pyridine) as a catalyst for intermolecular amination of C sp3 -H bonds of 9,10-dihydroanthracene (2 a) using 2,4,6-trimethyl phenyl azide (3 a) as the nitrene source. The reaction is complete within one hour at 80 °C using as low as 2 mol % 1-OEt 2 with control in selectivity for single C-H amination versus double C-H amination. Catalytic C-H amination reactions can be extended to other substrates such as cyclohexadiene and xanthene derivatives and can tolerate a variety of aryl azides having methyl groups in both ortho positions. Under stoichiometric conditions the imido radical species [( tBu pyrpyrr 2 )Fe{=N(2,6-Me 2 -4-tBu-C 6 H 2 )] (1-imido) can be isolated in 56 % yield, and spectroscopic, magnetometric, and computational studies confirmed it to be an S = 1 Fe IV complex. Complex 1-imido reacts with 2 a to produce the ferrous aniline adduct [( tBu pyrpyrr 2 )Fe{NH(2,6-Me 2 -4-tBu-C 6 H 2 )(C 14 H 11 )}] (1-aniline) in 45 % yield. Lastly, it was found that complexes 1-imido and 1-aniline are both competent intermediates in catalytic intermolecular C-H amination., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Although descriptions of quality of life and patient reports of mood in sickle cell disease (SCD) have become more common in the literature, less is known about psychiatric illness prevalence, presentation, and treatment, particularly for adults. We provide a narrative review of what is known about common and debilitating psychiatric conditions such as depression, anxiety, and cognitive impairment, specifically for adults with SCD. We discuss the limitations of the current evidence, make provisional recommendations, and identify opportunities for research and improved care., (© 2023 British Society for Haematology and John Wiley & Sons Ltd.)

The use of viral vectors for vaccine, gene therapy, and oncolytic virotherapy applications has received increased attention in recent years. Large-scale purification of viral vector-based biotherapeutics still presents a significant technical challenge. Chromatography is the primary tool for the purification of biomolecules in the biotechnology industry; however, the majority of chromatography resins currently available have been designed for the purification of proteins. In contrast, convective interaction media monoliths are chromatographic supports that have been designed and successfully utilized for the purification of large biomolecules, including viruses, viruslike particles, and plasmids. We present a case study on the development of a purification method for recombinant Newcastle disease virus directly from clarified cell culture media using strong anion exchange monolith technology (CIMmultus QA, BIA Separations). Resin screening studies showed at least 10 times higher dynamic binding capacity of CIMmultus QA compared to traditional anion exchange chromatography resins. Design of experiments was used to demonstrate a robust operating window for the purification of recombinant virus directly from clarified cell culture without any further pH or conductivity adjustment of the load material. The capture step was successfully scaled up from 1 mL CIMmultus QA columns to the 8 L column scale and achieved a greater than 30-fold reduction in process volume. Compared to the load material, total host cell proteins were reduced by more than 76%, and residual host cell DNA by more than 57% in the elution pool, respectively. Direct loading of clarified cell culture onto a high-capacity monolith stationary phase makes convective flow chromatography an attractive alternative to centrifugation or TFF-based virus purification procedures., (© 2023 Astrazeneca. Electrophoresis published by Wiley-VCH GmbH.)

Introduction: Integrated models of care intend to provide seamless and timely access to health and social care services. This study investigated the integration of musculoskeletal services across community and secondary care boundaries, including the introduction of a single point of access from which patients were triaged., Methods: Staff (n = 15) involved in service development and delivery were interviewed about how, why and to what extent integration impacted service delivery. The analysis focused on staff experiences of using an on-line patient self-referral form and co-located clinics to enhance decision-making in triage, and on the provision of educational materials and de-medicalising language in patient consultations to support self-management., Results: Single point of access, including online self-referral, were operationalised during data collection, but co-located clinics were not. Triage staff explained that the volume of referrals and quality of information provided in online self-referrals sometimes constrained decision-making in triage. Secondary care staff discussed concerns that the single point of access might not consistently identify patients with hard to diagnose conditions that require timely surgical intervention. This concern appeared to constrain staff engagement with integration, potentially inhibiting the delivery of co-located clinics. However, triage staff accessed support to inform secondary care referral via alternate modes. Patient circumstances, for example, need for reassurance, necessitated multiple self-management strategies and innovative approaches were developed to provide patients ongoing and professionally led support., Conclusion: Findings emphasise that restructuring services requires engagement from diverse stakeholders. Collaborating with stakeholders to address their concerns about the impact of restructures on well-established pathways may help cultivate this engagement., (© 2023 The Authors. Musculoskeletal Care published by John Wiley & Sons Ltd.)

We employ a metal-metal salt metathesis strategy to access low-valent tantalum-copper heterometallic architectures (Ta-μ 2 -H 2 -Cu and Ta-μ 3 -H 2 -Cu 3 ) that emulate structural elements proposed for surface alloyed nanomaterials. Whereas cluster assembly with carbonylmetalates is well precedented, the use of the corresponding polyarene transition metal anions is underexplored, despite recognition of these highly reactive fragments as storable sources of atomic M n- . Our application of this strategy provides structurally unique early-late bimetallic species. These complexes incorporate bridging hydride ligands during their syntheses, the origin of which is elucidated via detailed isotopic labelling studies. Modification of ancillary ligand sterics and electronics alters the mechanism of bimetallic assembly; a trinuclear complex resulting from dinuclear C-H activation is demonstrated as an intermediate en route to formation of the bimetallic. Further validating the promise of this rational, bottom-up approach, a unique tetranuclear species was synthesized, featuring a Ta centre bearing three Ta-Cu interactions., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

With an eye toward expanding chemistries used for covalent ligand discovery, we elaborated an umpolung strategy that exploits the 'polarity reversal' of sulfur when cysteine is oxidized to sulfenic acid, a widespread post-translational modification, for selective bioconjugation with C-nucleophiles. Here we present a global map of a human sulfenome that is susceptible to covalent modification by members of a nucleophilic fragment library. More than 500 liganded sulfenic acids were identified on proteins across diverse functional classes, and, of these, more than 80% were not targeted by electrophilic fragment analogs. We further show that members of our nucleophilic fragment library can impair functional protein-protein interactions involved in nuclear oncoprotein transport and DNA damage repair. Our findings reveal a vast expanse of ligandable sulfenic acids in the human proteome and highlight the utility of nucleophilic small molecules in the fragment-based covalent ligand discovery pipeline, presaging further opportunities using non-traditional chemistries for targeting proteins., (© 2023. The Author(s), under exclusive licence to Springer Nature America, Inc.)

Di- and multinuclear hafnium complexes bridged by ligands have been rarely reported. In this article, a novel 3,5-disubstituted pyrazolate-bridged ligand LH 5 with two [N 2 N] 2- -type chelating side arms was designed and synthesized, which supported a series of dinuclear hafnium complexes. Dinuclear hafnium azides [LHf 2 (μ-1,1-N 3 ) 2 (N 3 ) 2 ][Na(THF) 4 ] 3 and [LHf 2 (μ-1,1-N 3 ) 2 (N 3 ) 2 ][Na(2,2,2-Kryptofix)] 4 were further synthesized and structurally characterized, featuring two sets of terminal and bridging azido ligands like jellyfishes. The reactivity of 3 under reduction conditions was conducted, leading to a formation of a tetranuclear hafnium imido complex [L 1 Hf 2 (μ 1 -NH)(N 3 ){μ 2 -K}] 2 5. DFT calculations revealed that the mixed imido azide 5 was generated via an intramolecular C-H insertion from a putative dinuclear Hf IV -nitridyl intermediate., (© 2023 Wiley-VCH GmbH.)

Hox genes encode Homeodomain-containing transcription factors, which specify segmental identities along the anterior-posterior axis. Functional changes in Hox genes have been directly implicated in the evolution of body plans across the metazoan lineage. The Hox protein Ultrabithorax (Ubx) is expressed and required in developing third thoracic (T3) segments in holometabolous insects studied so far, particularly, of the order Coleoptera, Lepidoptera and Diptera. Ubx function is key to specify differential development of the second (T2) and T3 thoracic segments in these insects. While Ubx is expressed in the third thoracic segment in developing larvae of Hymenopteran Apis mellifera, the morphological differences between T2 and T3 are subtle. To identify evolutionary changes that are behind the differential function of Ubx in Drosophila and Apis, which are diverged for more than 350 million years, we performed comparative analyses of genome wide Ubx-binding sites between these two insects. Our studies reveal that a motif with a TAAAT core is a preferred binding site for Ubx in Drosophila, but not in Apis. Biochemical and transgenic assays suggest that in Drosophila, the TAAAT core sequence in the Ubx binding sites is required for Ubx-mediated regulation of two of its target genes studied here; CG13222, a gene that is normally upregulated by Ubx and vestigial (vg), whose expression is repressed by Ubx in T3. Interestingly, changing the TAAT site to a TAAAT site was sufficient to bring an otherwise unresponsive enhancer of the vg gene from Apis under the control of Ubx in a Drosophila transgenic assay. Taken together, our results suggest an evolutionary mechanism by which critical wing patterning genes might have come under the regulation of Ubx in the Dipteran lineage., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Secreted signaling molecules act as morphogens to control patterning and growth in many developing tissues. Since locally produced morphogens spread to form a concentration gradient in the surrounding tissue, spreading is generally thought to be the key step in the non-autonomous actions. Here, we review recent advances in tool development to investigate morphogen function using the role of decapentaplegic (Dpp)/bone morphogenetic protein (BMP)-type ligand in the Drosophila wing disc as an example. By applying protein binder tools to distinguish between the roles of Dpp spreading and local Dpp signaling, we found that Dpp signaling in the source cells is important for wing patterning and growth but Dpp spreading from this source cells is not as strictly required as previously thought. Given recent studies showing unexpected requirements of long-range action of different morphogens, manipulating endogenous morphogen gradients by synthetic protein binder tools could shed more light on how morphogens act in developing tissues., (© 2023 The Authors. BioEssays published by Wiley Periodicals LLC.)

The study of the redox chemistry of mid-actinides (U-Pu) has historically relied on cerium as a model, due to the accessibility of trivalent and tetravalent oxidation states for these ions. Recently, dramatic shifts of lanthanide 4+/3+ non-aqueous redox couples have been established within a homoleptic imidophosphorane ligand framework. Herein we extend the chemistry of the imidophosphorane ligand (NPC=[N=P t Bu(pyrr) 2 ] - ; pyrr=pyrrolidinyl) to tetrahomoleptic NPC complexes of neptunium and cerium (1-M, 2-M, M=Np, Ce) and present comparative structural, electrochemical, and theoretical studies of these complexes. Large cathodic shifts in the M 4+/3+ (M=Ce, U, Np) couples underpin the stabilization of higher metal oxidation states owing to the strongly donating nature of the NPC ligands, providing access to the U 5+/4+ , U 6+/5+ , and to an unprecedented, well-behaved Np 5+/4+ redox couple. The differences in the chemical redox properties of the U vs. Ce and Np complexes are rationalized based on their redox potentials, degree of structural rearrangement upon reduction/oxidation, relative molecular orbital energies, and orbital composition analyses employing density functional theory., (© 2023 Wiley-VCH Verlag GmbH.)

The COVID-19 pandemic has been shown to affect both physical and mental health. Because of this mental health burden, it is important to pay attention to issues such as the relationship between spiritual health, death attitudes and meaning in life - all issues made more prominent during the pandemic. This study was conducted to determine the correlation between these three factors - spiritual health, meaning in life, and death attitudes, among patients with COVID-19 discharged from the intensive care units of hospitals affiliated with Tehran University of Medical Sciences, Tehran, Iran.This cross-sectional, descriptive-analytical study was conducted between April 2020 and August 2021 with 260 participants. The data collection instruments were a demographic characteristics questionnaire, Polotzin and Ellison's Spiritual Health Questionnaire, The Meaning in Life Questionnaire (MLQ), and Death Attitude Profile-Revised (DAP-R).The correlation between meaning in life, spiritual health, and death attitudes was determined by Spearman's correlation coefficient. The research results showed that there is an inverse and significant correlation between spiritual health and death attitudes (p = 0.01); an inverse, but insignificant correlation between existential health and subscales of death attitudes, except for the subscales of approach acceptance and neutral acceptance (p > 0.05); and an inverse, but insignificant, correlation between spiritual health and death attitudes, (p > 0.05). In addition, there was an inverse and significant correlation between the presence of meaning in life and escape acceptance (p = 0.002); an inverse and significant correlation between the search for meaning in life and neutral acceptance (p = 0.007); and an inverse and significant correlation between the meaning in life and death attitudes (p = 0.04). Besides, the findings showed an inverse but insignificant correlation between all spiritual health subscales and the meaning in life subscales (p > 0.05). Spiritual health has an inverse correlation with death attitudes.Also, there is an inverse correlation between the total score of spiritual health and death attitudes. Regarding the subscales of spiritual health, there is an inverse correlation between existential health and death attitudes subscales, except for approach acceptance and neutral acceptance. Also, the results showed an inverse and significant correlation between meaning in life and death acceptance and avoidance subscales, and there was an inverse and significant correlation between the meaning in life and death attitudes. Finally, the increase in spiritual health reduces patients' risks of thinking about death. The research results double the significance of the role of nurses, especially those dealing with critically ill patients and those who have experienced severe disease conditions., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)