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The reaction of one equivalent of zinc(II) halide salts with two equivalents of isoquinoline N-oxide (iQNO; C9H7NO) in methanol yields compounds of the general formula [ZnX2(iQNO)2], with X = Cl− (I), Br− (II) and I− (III). However, starting with zinc(II) perchlorate or nitrate leads to the formation of complex ions with the compositions [Zn(iQNO)6](X)2 for X = ClO4− (IV), and [Zn(iQNO)(H2O)5](iQNO)2X2 for X = NO3− (V). Complexes (I), (II) and (III), namely dichloridobis(isoquinoline N-oxide-κO)zinc(II) [ZnCl2(C9H7NO)2], dibromidobis(isoquinoline N-oxide-κO)zinc(II) [ZnBr2(C9H7NO)2], and diiodidobis(isoquinoline N-oxide-κO)zinc(II) [ZnI2(C9H7NO)2], each exhibit a distorted tetrahedral coordination geometry around the zinc(II) ion coordinated by two iQNO ligands bound through the oxygen atom and two halide ions. The zinc ion lies on a crystallographic twofold axis in the bromo complex. The X—Zn—X bond angles are approximately 15–17° larger than the O—Zn—O bond angles resulting in the observed tetrahedral distortion. In complex (IV), hexakis(isoquinoline N-oxide-κO)zinc(II) bis(perchlorate), [Zn(C9H7NO)6](ClO4)2, the zinc(II) ion occupies a special position with 3 site symmetry and is octahedrally coordinated by six iQNO ligands, albeit with slight distortions evidenced by a spread of cis bond angles from 85.82 (4) to 94.18 (4)°. The chlorine atom of the perchlorate anion lies on a crystallographic threefold axis. Finally, complex (V) crystallizes with a pseudo-octahedral geometry; pentaaqua(isoquinoline N-oxide-κO)zinc(II) dinitrate–isoquinoline N-oxide (1/2), [Zn(C9H7NO)(H2O)5](NO3)2·2(C9H7NO). The nitrate ions and non-coordinated iQNO molecules engage in π-stacking and hydrogen-bonding interactions with the coordinated water molecules. The iQNO—Zn—O equatorial bond angles range from 88.98 (9) to 94.90 (9)°, with the largest deviation from a perfect octahedral angle attributed to the influence of a weak C—H...O (from water) interaction (2.287 Å) involving the bound iQNO ligand.

The reactions of triphenylsulfonium chloride ([TPS][Cl]) with various acids in methanol yield the corresponding salts triphenylsulfonium triiodide, C18H15S+·I3− or [TPS][I3] (I), triphenylsulfonium perchlorate, C18H15S+·ClO4− or [TPS][ClO4] (II), and triphenylsulfonium hexafluorophosphate, C18H15S+·PF6− or [TPS][PF6] (III), as crystalline products. These crystals were structurally characterized by single-crystal X-ray diffraction. In all three compounds, the sulfur atom in the triphenylsulfonium cation adopts a distorted trigonal–pyramidal geometry. [TPS][I3] (I) and [TPS][PF6] (III) both crystallize in the space group P21/n, while [TPS][ClO4] (II) crystallizes in P21. The S—C bond lengths are comparable across the three salts, and the S—C—S bond angles are consistently between 102 and 106°. Hirshfeld surface analyses reveal that each structure is dominated by hydrogen-based intermolecular contacts, supplemented by anion-specific interactions such as I...H in (I), O...H in (II), and F...H in (III). These contacts organize the ions into mono-periodic ribbon- or chain-like arrangements. No significant π–π stacking is observed.

In this study, we examined how technology impacts adolescents' perceptions of, and affective responses to solitude, as well as how adolescents' own motivations for solitude (shyness, affinity for aloneness) were related to these reactions. Participants were N = 437 adolescents (297 girls; M[subscript age] = 16.15 years, standard deviation (SD) = 0.50) who were presented with a series of hypothetical vignettes asking them to imagine themselves in the context of pure solitude (alone in their room with the door closed), as well as being physically alone but engaged in increasing levels of virtual social engagement, including passive (e.g., watching videos, scrolling, but no direct social engagement), active (e.g., texting), and audio-visual (e.g., Facetime) technology use. Following each vignette, participants reported their perceptions of being alone and positive/negative affective responses. We also measured general motivations for solitude (shyness, affinity for aloneness). Among the results, adolescents perceived themselves as less alone in vignettes depicting increasing virtual social engagement. Affective benefits of increased virtual engagement were also found (e.g., less loneliness/boredom/sadness, greater social connection/contentment). However, these effects were moderated by solitude motivations, with different patterns evident as a function of participant shyness and affinity for aloneness. Findings highlight the importance of considering the nature of adolescents' technology use when alone, as well as motivations for solitude, when considering links between solitude and well-being.

The reaction of one equivalent of zinc(II) halide with two equivalents of quinoline N-oxide (QNO) in methanol yields compounds as ZnX2(QNO)2, where X = Cl (I), Br (II) and I (III), namely, dichloridobis(quinoline N-oxide-κO)zinc(II), [ZnCl2(C9H7NO)2], dibromidobis(quinoline N-oxide-κO)zinc(II), [ZnBr2(C9H7NO)2], and diiodidobis(quinoline N-oxide-κO)zinc(II) [ZnI2(C9H7NO)2]. In all three complexes, Zn cations are coordinated by two QNO ligands bound through the oxygen atoms and two halide atoms, with X—Zn—X bond angles ca 20° wider than the O—Zn—O, giving rise to a distorted tetrahedral geometry. Crystals of (II) and (III) are isostructural and both show pairwise π-stacking of QNO ligands and weak C—H...X hydrogen bonds, while (I) packs differently, with a shorter C—H...Cl bond and without π-stacking.

The reactions of triphenylsulfonium chloride ([TPS][Cl]) with various acids in methanol yield the corresponding salts triphenylsulfonium triiodide, C18H15S+ ·- I3 or [TPS][I3] (I), triphenylsulfonium perchlorate, C18H15S+ ·ClO4 or [TPS][ClO4] (II), and triphenylsulfonium hexafluorophosphate, C18H15S+ ·PF6 or [TPS][PF6] (III), as crystalline products. These crystals were structurally characterized by single-crystal X-ray diffraction. In all three compounds, the sulfur atom in the triphenylsulfonium cation adopts a distorted trigonal–pyramidal geometry. [TPS][I3] (I) and [TPS][PF6] (III) both crystallize in the space group P21/n, while [TPS][ClO4] (II) crystallizes in P21. The S—C bond lengths are comparable across the three salts, and the S—C—S bond angles are consistently between 102 and 106°. Hirshfeld surface analyses reveal that each structure is dominated by hydrogen-based intermolecular contacts, supplemented by anion-specific interactions such as I··· H in (I), O ··· H in (II), and F ··· H in (III). These contacts organize the ions into mono-periodic ribbon- or chain-like arrangements. No significant π - π stacking is observed. [ABSTRACT FROM AUTHOR]

The reaction of one equivalent of zinc(II) halide salts with two equivalents of iso­quinoline N-oxide (iQNO; C9H7NO) in methanol yields compounds of the general formula [ZnX2(iQNO)2], with X = Cl− (I), Br− (II) and I− (III). However, starting with zinc(II) perchlorate or nitrate leads to the formation of complex ions with the compositions [Zn(iQNO)6](X)2 for X = ClO4− (IV), and [Zn(iQNO)(H2O)5](iQNO)2X2 for X = NO3− (V). Complexes (I), (II) and (III), namely di­chlorido­bis­(iso­quinoline N-oxide-κO)zinc(II) [ZnCl2(C9H7NO)2], di­bromido­bis­(iso­quinoline N-oxide-κO)zinc(II) [ZnBr2(C9H7NO)2], and di­iodido­bis­(iso­quinoline N-oxide-κO)zinc(II) [ZnI2(C9H7NO)2], each exhibit a distorted tetra­hedral coordination geometry around the zinc(II) ion coordinated by two iQNO ligands bound through the oxygen atom and two halide ions. The zinc ion lies on a crystallographic twofold axis in the bromo complex. The X—Zn—X bond angles are approximately 15–17° larger than the O—Zn—O bond angles resulting in the observed tetra­hedral distortion. In complex (IV), hexa­kis­(iso­quinoline N-oxide-κO)zinc(II) bis­(perchlorate), [Zn(C9H7NO)6](ClO4)2, the zinc(II) ion occupies a special position with 3 site symmetry and is octa­hedrally coordinated by six iQNO ligands, albeit with slight distortions evidenced by a spread of cis bond angles from 85.82 (4) to 94.18 (4)°. The chlorine atom of the perchlorate anion lies on a crystallographic threefold axis. Finally, complex (V) crystallizes with a pseudo-octa­hedral geometry; penta­aqua­(iso­quinoline N-oxide-κO)zinc(II) dinitrate–iso­quinoline N-oxide (1/2), [Zn(C9H7NO)(H2O)5](NO3)2·2(C9H7NO). The nitrate ions and non-coordin­ated iQNO mol­ecules engage in π-stacking and hydrogen-bonding inter­actions with the coordinated water mol­ecules. The iQNO—Zn—O equatorial bond angles range from 88.98 (9) to 94.90 (9)°, with the largest deviation from a perfect octa­hedral angle attributed to the influence of a weak C—H⋯O (from water) inter­action (2.287 Å) involving the bound iQNO ligand. [ABSTRACT FROM AUTHOR]

The aim of this short-term longitudinal study was to explore the moderating role of insecure mother--child attachment (i.e., ambivalent and avoidant) in the relations between shyness and indices of adjustment difficulties in early childhood. Participants were 360 children (200 boys and 160 girls, M[subscript age]=4.72 years, SD=0.63) attending preschools/kindergartens in Shanghai, People's Republic of China. At Time 1, mothers rated children's shyness and insecure attachment. At Time 2, 1½ years later, teachers assessed children's adjustment outcomes at school. Among the results, shyness was negatively associated with sociability, social competence, and internalizing problems. However, both ambivalent and avoidant insecure attachment significantly moderated these associations, exacerbating the relations between shyness and indices of adjustment difficulties. Results are discussed in terms of the contributions of attachment to young shy children's adjustment outcomes.

Sentiment analysis is a computational method that automatically analyzes the valence of massive quantities of text. Basic sentiment analysis involves extracting and counting emotionally-laden keywords from passages of text (e.g., "hate," "love," "happy," "sad"). This study describes using sentiment analysis to explore changes in emotion expression in a developmental context. A sample of n = 8,688 poems published online by children and adolescents from Grade 4 to Grade 12 was analyzed. Sentiment analysis coded words as positive or negative and these were averaged within each poem to obtain its relative percentage of positive and negative sentiment. Polynomial regressions explored linear and nonlinear trends in sentiment scores by grade. Among the results, negative sentiment demonstrated an upward curvilinear trend, increasing sharply from Grade 6 to Grade 11 and then decreasing afterward. Positive sentiment demonstrated a sinusoidal pattern throughout development. Overall, these findings are consistent with previous research on the progressions of emotion expression in childhood and adolescence. Despite some limitations, sentiment analysis presents an opportunity for researchers in developmental psychology to explore basic questions in emotional development using large quantities of data.

Background: While delays in cognitive development are detectable during early development in Down syndrome, the neuropsychological and biomedical underpinnings of cognitive skill acquisition in this population remain poorly understood. Method: To explore this issue, 38 infants with Down syndrome [mean chronological age = 9.65 months; SD = 3.64] completed the Bayley Scales of Infant Development-III and a set of laboratory tasks that measured sustained attention (duration of visual attention during a 1-min object exploration task), attention shifting (mean latency to shift attention on an alternating object presentation task) and visual short-term memory (dishabituation to a novel object on a change preference task). Results: Latency to shift attention was negatively associated with Bayley Cognitive Scale raw scores, even when controlling for the effects of chronological age, r (33) = -0.41, P = 0.02. In addition, prematurity status was associated with latency to shift attention. Conclusions: Early attention shifting may be an important factor that facilitates overall cognitive skill acquisition in infants with Down syndrome, and premature birth may be a risk factor for difficulties on this dimension.

We present a fourth-order finite-volume algorithm in space and time for low Mach number reacting flow with detailed kinetics and transport. Our temporal integration scheme is based on a Multi-Implicit Spectral Deferred Correction (MISDC) strategy that iteratively couples advection, diffusion, and reactions evolving subject to a constraint. Our new approach overcomes a stability limitation of our previous second-order method encountered when trying to incorporate higher-order polynomial representations of the solution in time to increase accuracy. We have developed a new iterative scheme that naturally fits within our MISDC framework and allows us to conserve mass and energy while simultaneously satisfying the equation of state. We analyse the conditions for which the iterative schemes are guaranteed to converge to the fixed point solution. We present numerical examples illustrating the performance of the new method on premixed hydrogen, methane, and dimethyl ether flames.

ABSTRACT Butorphanol–Azaperone–Medetomidine (BAM) is a relatively new drug mixture compounded for the past decade to immobilize mammals, particularly ungulates. Despite its increased use in recent years, scant research has quantified the physiologic responses of immobilized animals or assessed its relative efficacy using different trapping methods. We tested the safety and efficacy of BAM for use in the immobilization of 198 free‐ranging white‐tailed deer (Odocoileus virginianus) captured using drop‐nets, Clover traps, and gun‐propelled darts from 1 January 2014 to 28 July 2016 in Kentucky and Indiana, USA. Use of BAM produced a safe and satisfactory plane of immobilization that rarely required treatment of side effects. First signs of induction were observed on average at 4.4 ± 0.2 (standard error) minutes post–intramuscular administration, and deer reached lateral recumbency at 8.6 ± 0.4 minutes. Times to first signs of induction and the induction period were longer for adults than for juveniles, while times to the first sign of reversal, lifting head, and standing were longer for juveniles than adults. Although physiologic responses of deer during induction were within published norms, respiration rates, body temperature, heart rates, and oxygen saturation typically declined throughout the immobilization period. Our BAM dose did not affect time to recovery or heart rate. Regardless of trapping method, on average, heart rate was 61.2 ± 0.7 beats/minute, respiratory rate was 29.1 ± 0.5 breaths/minute, temperature was 38.93° ± 0.04° C, and oxygen saturation was 85.0% ± 0.3%. Deer showed first signs of reversal at 4.3 ± 0.3 minutes after administration of the reversal agent intramuscularly or half‐intramuscularly and half‐intravenously and were fully recovered after 6.3 ± 0.4 minutes. In summary, we found that BAM was an efficacious and safe drug to use on white‐tailed deer captured by a variety of trapping methods. © 2020 The Wildlife Society.

Accurate forecasts of weather conditions have the potential to mitigate the social and economic damages they cause. To make informed decisions based on forecasts, it is important to determine the extent to which they could be skillful. This study focuses on subseasonal forecasts out to a lead time of four weeks. We examine the differences between the potential predictability, which is computed under the assumption of a "perfect model," of integrated vapor transport (IVT) and precipitation under extreme conditions in subseasonal forecasts across the northeast Pacific. Our results demonstrate significant forecast skill of extreme IVT and precipitation events (exceeding the 90th percentile) into week 4 for specific areas, particularly when anomalously wet conditions are observed in the true model state. This forecast skill during weeks 3 and 4 is closely associated with a zonal extension of the North Pacific jet. These findings of the source of skillful subseasonal forecasts over the U.S. West Coast could have implications for water management in these regions susceptible to drought and flooding extremes. Additionally, they may offer valuable insights for governments and industries on the U.S. West Coast seeking to make informed decisions based on extended weather prediction. Significance Statement: The purpose of this study is to understand the differences between the ability to predict high amounts of the transport of water vapor and precipitation over the North Pacific 3 and 4 weeks into the future. The results indicate that differences do exist in a region that is relevant to precipitation on the U.S. West Coast. To physically explain why differences in predictability exist, the relationship between weekly extremes of the extension of the jet stream, IVT, and precipitation over the North Pacific is explored. These findings may impact decisions relevant to water management on the U.S. West Coast susceptible to drought and flooding extremes. [ABSTRACT FROM AUTHOR]

Four manganese(II) bromide coordination complexes have been prepared with four pyridine N-oxides, viz. pyridine N-oxide (PNO), 2-methylpyridine N-oxide (2MePNO), 3-methylpyridine N-oxide (3MePNO), and 4-methylpyridine N-oxide (4MePNO). The compounds are bis(μ-pyridine N-oxide)bis[aquadibromido(pyridine N-oxide)manganese(II)], [Mn2Br4(C5H5NO)4(H2O)2] (I), bis(μ-2-methylpyridine N-oxide)bis[diaquadibromidomanganese(II)]–2-methylpyridine N-oxide (1/2), [Mn2Br4(C6H7NO)2(H2O)4]·2C6H7NO (II), bis(μ-3-methylpyridine N-oxide)bis[aquadibromido(3-methylpyridine N-oxide)manganese(II)], [Mn2Br4(C6H7NO)4(H2O)2] (III), and bis(μ-4-methylpyridine N-oxide)bis[dibromidomethanol(4-methylpyridine N-oxide)manganese(II)], [Mn2Br4(C6H7NO)4(CH3OH)2] (IV). All the compounds have one unique MnII atom and form a dimeric complex that contains two MnII atoms related by a crystallographic inversion center. Pseudo-octahedral six-coordinate manganese(II) centers are found in all four compounds. All four compounds form dimers of Mn atoms bridged by the oxygen atom of the PNO ligand. Compounds I, II and III exhibit a bound water of solvation, whereas compound IV contains a bound methanol molecule of solvation. Compounds I, III and IV exhibit the same arrangement of molecules around each manganese atom, ligated by two bromide ions, oxygen atoms of two PNO ligands and one solvent molecule, whereas in compound II each manganese atom is ligated by two bromide ions, one O atom of a PNO ligand and two water molecules with a second PNO molecule interacting with the complex via hydrogen bonding through the bound water molecules. All of the compounds form extended hydrogen-bonding networks, and compounds I, II, and IV exhibit offset π-stacking between PNO ligands of neighboring dimers.

Research Findings: The aim of the present study was to examine the moderating role of inhibitory control (IC) in the associations between shyness and young children's social and school adjustment. Participants were 112 Italian children (M = 56.85 months, SD = 10.14) enrolled in preschool. Parents and teachers assessed child shyness and IC as well as indices of social and school adjustment. Children were interviewed to assess vocabulary. Results from hierarchical multiple regression analyses revealed several significant interaction effects between shyness and IC in the prediction of outcome variables. Follow-up simple slope analyses indicated that among children with higher levels of IC, shyness was negatively related to prosocial behavior and popularity. In contrast, among children with lower levels of IC, shyness was positively associated with regulated school behaviors. Practice or Policy: The findings provide evidence to suggest that the combination of shyness and IC may contribute to children's behavioral rigidity, which in turn may promote social and school adjustment difficulties.