The Synthesis, Structural Characterization, and DFT Calculation of a New Binuclear Gd(III) Complex with 4-Aacetylphenoxyacetic Acid and 1,10-Phenanthroline Ligands and Its Roles in Catalytic Activity.

A new binuclear Gd(III) complex, [Gd2(L)6(Phen)2]·4H2O, was synthesized via the reaction of gadolinium(III) nitrate hexahydrate, 4-acetylphenoxyacetic acid (HL), NaOH, and 1,10-phenanthroline (Phen) in a solution of water-ethanol (v:v = 1:1). The Gd(III) complex was characterized using IR, UV-vis, TG-DSC, fluorescence, and single-crystal X-ray diffraction analyses. The results showed that the Gd(III) complex crystallizes in the triclinic system, space group P-1, and each Gd(III) ion was coordinated with two nitrogen atoms (N1, N2, or N1a, and N2a) from two Phen ligands and seven oxygen atoms (O1, O2, O7a, O9, O8, O8a, O10a, or O1a, O2a, O7, O8, O8a, O9a, and O10) from six L ligands, respectively, forming a nine-coordinated coordination mode. The Gd(III) complex molecules formed a one-dimensional chained and three-dimensional network structure via benzenering π-π stacking. The Hirschfeld surface analysis and the calculations of the electron density distributions of the frontier molecular orbitals of the Gd(III) complex were performed. The catalytic activities of the photocatalytic CO2 reduction and benzyl alcohol oxidation using the Gd(III) complex as a catalyst were performed. The results of the photocatalytic CO2 reduction showed that the yield and the selectivity of CO reached 41.5 µmol/g and more than 99% after four hours, respectively. The results of the benzyl alcohol oxidation showed that the yield of benzaldehyde was 45.7% at 120 °C with THF as the solvent under 0.5 MPa O2 within 2 h.

Giving It a Shot with a Different Approach: Prosocial Strategies Moderate the Joint Effects of Agentic and Communal Goals on Bullying.

This study uses polynomial regression and response surface analyses to investigate the joint effects of agentic and communal goals on bullying and the moderating role of prosocial strategies. The sample included 917 adolescents (Mage = 13.54, SD = 1.02) from rural, suburban, and urban areas in China. The findings revealed that higher agentic and lower communal goals were associated with a linear rise in bullying. Surprisingly, when both social goals were higher simultaneously, bullying followed an inverted U-shaped pattern. Furthermore, prosocial strategies moderated the joint effects of the two social goals. Adolescents who are more likely to use prosocial strategies do not show significant changes in bullying when both goals are at a higher level. In contrast, those who are less likely to do so show a linear rise in bullying, regardless of changes in social goals. This study improves our understanding and intervention of bullying behavior, emphasizing a non-pathological perspective.

How Needs-Supplies Fit Processes With Teachers, Peers, and Parents Relate to Youth Outcomes: A Theoretical and Methodological Extension of Self-Determination Theory.

According to self-determination theory (SDT), relationships that support the needs for autonomy, competence, and relatedness are essential to youth development. It is yet unknown whether adolescents differ in what constitutes "optimal" supplies of support. This research proposes methodological extensions to analyze how the degree of fit or misfit between needs versus supplies in support (i.e., from teachers, parents, and peers) relates to engagement in class, academic achievement, and well-being. Data were collected on 389 adolescents (M(age) = 14.3, SD(age) = 2.1, 58% female, low to high SES). Extending SDT's contention that "the more supplies the better", results suggest that the impact of supplies actually depends on the level of needs, and that commensurate (for parents) or surplus supplies (for teachers, peers) are most optimal. Therefore, while some youth require strongly supportive relationships to experience optimal development, others require much lower support, and may even suffer from higher support.

Solvent Effect on Dative and Ionic Bond Strengths: A Unified Theory from the Potential Analysis and Valence Bond (VB) Computation.

Solvent molecules interact with a solute through various intermolecular forces. Here we employed a potential energy surface (PES) analysis to interpret the solvent-induced variations in the strengths of dative (Me3NBH3) and ionic (LiCl) bonds, which possess both ionic and covalent (neutral) characteristics. The change of a bond is driven by the gradient (force) of the solvent-solute interaction energy with respect to the focused bond length. Positive force shortens the bond length and increases the bond force constant, leading to a blue-shift of the bond stretching vibrational frequency upon solvation. Conversely, negative force elongates the bond, resulting in a reduced bond force constant and red-shift of the stretching vibrational frequency. The different responses of Me3NBH3 and LiCl to solvation are studied with valence bond (VB) theory, as Me3NBH3 and LiCl are dominated by the neutral covalent VB structure and the ionic VB structure, respectively. The dipole moment of an ionic VB structure increases along the increasing bond distance, while the dipole moment of a neutral covalent VB structure increases with the decreasing bond distance. The roles of the dominating VB structures are further examined by the geometry optimizations and frequency calculations with the block-localized wavefunction (BLW) method.

Wear Mechanisms of the Working Surface of Gears after Scuffing Tests.

Identification of changes occurring on the working surface of lubricated gears using analytical equipment, e.g., an FE-SEM scanning electron microscope with an EDS microanalyzer, a WLI interferometric microscope, or a GDEOS optical discharge spectrometer, enables the characterisation of wear mechanisms of this surface. Definition of the phenomena occurring on the surface of tribo-couples after scuffing tests enables a comparative analysis of scuffing resistance and surface properties of the micro- and nanostructure, and elemental composition of the tested gears. Recognition and analysis of the wear mechanisms occurring on the working surface of gears will reduce the risk of damage and losses resulting from the need for maintenance and repair. The study concerned the working surfaces of gears made of 17HNM and 35HGSA steels on which a W-DLC/CrN coating was deposited. Shell Omala S4 GX 320 commercial industrial oil with a synthetic PAO (polyalphaolefin) base was selected for the lubrication of the gears. Tribological tests employed an FZG gear scuffing under severe conditions test method and they were carried out on a T-12U test rig for cylindrical gear analysis.

Crystal structure and Hirshfeld surface analysis of dimeth-yl(phen-yl)phosphine sulfide.

The title compound, C8H11PS, which melts below room temperature, was crystallized at low temperature. The P-S bond length is 1.9623 (5) Šand the major contributors to the Hirshfeld surface are H⋯H (58.1%), S⋯H/H⋯S (13.4%) and C⋯H/H⋯C contacts (11.7%).

Crystal structure and Hirshfeld surface analysis of 1-[6-bromo-2-(4-fluoro-phen-yl)-1,2,3,4-tetra-hydroquinolin-4-yl]pyrrolidin-2-one.

In the title compound, C19H18BrFN2O, the pyrrolidine ring adopts an envelope conformation. In the crystal, mol-ecules are linked by inter-molecular N-H⋯O, C-H⋯O, C-H⋯F and C-H⋯Br hydrogen bonds, forming a three-dimensional network. In addition, C-H⋯π inter-actions connect mol-ecules into ribbons along the b-axis direction, consolidating the mol-ecular packing. The inter-molecular inter-actions in the crystal structure were qu-anti-fied and analysed using Hirshfeld surface analysis.

Crystal structure and Hirshfeld surface analysis of 6,6'-dimethyl-2,2'-bi-pyridine-1,1'-diium tetra-chlorido-cobaltate(II).

In the title mol-ecular salt, (C12H14N2)[CoCl4], the dihedral angle between the pyridine rings of the cation is 52.46 (9)° and the N-C-C-N torsion angle is -128.78 (14)°, indicating that the ring nitro-gen atoms are in anti-clinal conformation. The Cl-Co-Cl bond angles in the anion span the range 105.46 (3)-117.91 (2)°. In the extended structure, the cations and anions are linked by cation-to-anion N-H⋯Cl and C-H⋯Cl inter-actions, facilitating the formation of R 4 4(18) and R 4 4(20) ring motifs. Furthermore, the crystal structure features weak anion-to-cation Cl⋯π inter-actions [Cl⋯π = 3.4891 (12) and 3.5465 (12) Å]. Hirshfeld two-dimensional fingerprint plots revealed that the most significant inter-actions are Cl⋯H/H⋯Cl (45.5%), H⋯H (29.0%), Cl⋯C/C⋯Cl (7.8%), Cl⋯N/N⋯Cl (3.5%), Cl⋯Cl (1.4) and Co⋯H (1%) contacts.

Crystal structure and Hirshfeld surface analysis of 2-bromo-ethyl-ammonium bromide - a possible side product upon synthesis of hybrid perovskites.

This study presents the synthesis, characterization and Hirshfeld surface analysis of a small organic ammonium salt, C2H7BrN+·Br-. Small cations like the one in the title compound are considered promising components of hybrid perovskites, crucial for optoelectronic and photovoltaic applications. While the incorporation of this organic cation into various hybrid perovskite structures has been explored, its halide salt counterpart remains largely uninvestigated. The obtained structural results are valuable for the synthesis and phase analysis of hybrid perovskites. The title compound crystallizes in the solvent-free form in the centrosymmetric monoclinic space group P21/c, featuring one organic cation and one bromide anion in its asymmetric unit, with a torsion angle of -64.8 (2)° between the ammonium group and the bromine substituent, positioned in a gauche conformation. The crystal packing is predominantly governed by Br⋯H inter-actions, which constitute 62.6% of the overall close atom contacts.

Synthesis, structure and Hirshfeld surface analysis of 2-oxo-2H-chromen-4-yl penta-noate.

In the title compound, C14H14O4, the dihedral angle between the coumarin ring system (r.m.s deviation = 0.016 Å) and the penta-noate ring is 36.26 (8)°. A short intra-molecular C-H⋯O contact of 2.40 Šis observed. Hirshfeld surface analysis reveals that 46.1% of the inter-molecular inter-actions are from H⋯H contacts, 28.6% are from H⋯O/O⋯H contacts and 14.7% are from H⋯C/C⋯H.

Crystal structure and Hirshfeld surface analysis of a halogen bond between 2-(allyl-thio)-pyridine and 1,2,4,5-tetra-fluoro-3,6-di-iodo-benzene.

The crystal structure of the title 2:1 mol-ecular complex between 2-(allyl-thio)-pyridine and 1,2,4,5-tetra-fluoro-3,6-di-iodo-benzene, C6F4I2·2C8H9NS, at 100 K has been determined in the monoclinic space group P21/c. The most noteworthy characteristic of the complex is the halogen bond between iodine and the pyridine ring with a short N⋯I contact [2.8628 (12) Å]. The Hirshfeld surface analysis shows that the hydrogen⋯hydrogen contacts dominate the crystal packing with a contribution of 32.1%.

How Parental Mediation and Parental Phubbing Affect Preschool Children's Screen Media Use: A Response Surface Analysis.

Parental mediation (PM) and parental phubbing (PP) are two pivotal factors that influence children's screen media use. This study used response surface analysis to examine the combined effect of PM and PP on screen time among preschool children. A total of 3,445 parents with preschool-aged children participated in this study, providing self-reported data on PM, PP, and their children's screen time (CST). The results revealed that CST decreased when parents enhanced their mediation behaviors and reduced phubbing behaviors in the cases of congruence between PM and PP. In instances of incongruence, reduced screen time was observed when parents exhibited lower frequency in mediating their CST and displayed fewer phubbing behaviors compared with situations where parents mediated their children more frequently but engaged in higher levels of phubbing behaviors. The findings suggest that PM play a significant role in mitigating preschool-aged children's excessive screen time. Moreover, it is critical to establish positive role modeling by reducing PP behaviors.

Discrepancies in Parent-Child Perception of Parental Control and Associations with Children's Anxiety: The Buffering Effect of Parent-Child Closeness.

Previous research has predominantly relied on single-informant reports to establish the association between parental control and children's anxiety. However, there remains ambiguity regarding the extent to which discrepancies in parent-child reports of parental control are related to children anxiety. This study examined parent-child perceived discrepancies in parental control and their association with children's anxiety, along with the moderated effect of parent-child closeness through cross-sectional and prospective analysis. The sample consisted of 790 children (Mage = 11.34, SD = 6.73, 45.60% for girls), with 741 father-child dyads and 760 mother-child dyads included. Data were analyzed using polynomial regressions with response surface analysis. The results indicated that children tended to perceive higher levels of parental psychological control and lower levels of behavioral control compared to their parents' perceptions. In the cross-sectional analysis, a significant association between greater incongruence in psychological/behavioral control and higher levels of children's anxiety at T1 was observed exclusively in father-child dyads. In prospective analysis, for both father-child and mother-child dyads, congruence in higher levels of psychological control was associated with higher levels of children's anxiety at T2, while congruence in higher levels of behavioral control was associated with lower levels of children's anxiety at T2. Additionally, greater incongruence in psychological/behavioral control was linked to higher levels of children's anxiety at T2. Furthermore, mother-child closeness emerged as a significant moderator such that perceived incongruence in psychological/behavioral control could not affect children's anxiety at T2 in the high mother-child closeness condition. These findings highlight the significance of considering parent-child congruence and incongruence when examining the impact of parental control on children's anxiety.

Social support and family resilience among Chinese people receiving maintenance hemodialysis: A polynomial regression and response surface analysis explaining psychological resilience.

Psychological resilience plays an important role in overcoming emotional distress among people receiving maintenance hemodialysis (MHD). This study aimed to investigate how social support and family resilience interact to influence psychological resilience among Chinese people receiving MHD. This was a prospective longitudinal study with three time points: baseline (T1), 3 months (T2), and 6 months (T3) later. A convenience sample of 252 participants (67.1% male; 57.6 ± 13.8 years of age) from Zhejiang Province, China, who completed baseline measures of social support, family resilience, and psychological resilience, were further assessed for psychological resilience at T2 and T3. Polynomial regression (PR) and response surface analysis (RSA) were used to analyze the data. At all time points, and in the case of agreement between social support and family resilience, the combined effect of both variables manifested as a positive linear association with psychological resilience. Instead, at baseline, and in case of disagreement, the same combined effect manifested as a negative linear relationship related to psychological resilience. The findings highlighted the importance of considering the conjoint influence of social support and family resilience when developing interventions to improve the psychological resilience of people receiving MHD.

Assessing brain neuroplasticity: Surface morphometric analysis of cortical changes induced by Quadrato motor training.

Morphological markers for brain plasticity are still lacking and their findings are challenged by the extreme variability of cortical brain surface. Trying to overcome the "correspondence problem," we applied a landmark-free method (the generalized procrustes surface analysis (GPSA)) for investigating the shape variation of cortical surface in a group of 40 healthy volunteers (i.e., the practice group) subjected to daily motor training known as Quadrato motor training (QMT). QMT is a sensorimotor walking meditation that aims at balancing body, cognition, and emotion. More specifically, QMT requires coordination and attention and consists of moving in one of three possible directions on corners of a 50 × 50 cm2. Brain magnetic resonance images (MRIs) of practice group (acquired at baseline, as well as after 6 and 12 weeks of QMT), were 3D reconstructed and here compared with brain MRIs of six more volunteers never practicing the QMT (naïve group). Cortical regions mostly affected by morphological variations were visualized on a 3D average color-scaled brain surface indicating from higher (red) to lower (blue) levels of variation. Cortical regions interested in most of the shape variations were as follows: (1) the supplementary motor cortex; (2) the inferior frontal gyrus (pars opercolaris) and the anterior insula; (3) the visual cortex; (4) the inferior parietal lobule (supramarginal gyrus and angular gyrus). Our results show that surface morphometric analysis (i.e., GPSA) can be applied to assess brain neuroplasticity processes, such as those stimulated by QMT.

Birth expectations, birth experiences and childbirth-related post-traumatic stress symptoms in mothers and birth companions: Dyadic investigation using response surface analysis.

OBJECTIVES: During the perinatal period, women and their birth companions form expectations about childbirth. We aimed to examine whether a mismatch between birth expectations and experiences predict childbirth-related post-traumatic stress symptoms (CB-PTSS) for mothers and birth companions. We also explored the influence of the mismatch between mothers' and birth companions' expectations/experiences on CB-PTSS. DESIGN: Dyadic longitudinal data from the Self-Hypnosis IntraPartum Trial. METHODS: Participants (n = 469 mothers; n = 358 birth companions) completed questionnaires at 27 and 36 weeks of gestation and 2 and 6 weeks post-partum. We used the measures of birth expectations (36 weeks gestation), birth experiences (2 weeks post-partum) and CB-PTSS (6 weeks post-partum). RESULTS: Correlations revealed that birth expectations were associated with experiences for both mothers and birth companions but were not consistently associated with CB-PTSS. Birth experiences related to CB-PTSS for both mothers and birth companions. The response surface analysis results showed no support for the effect of a mismatch between expectations and experiences on CB-PTSS in mothers or birth companions. Similarly, a mismatch between mothers' and birth companions' expectations or experiences was unrelated to CB-PTSS. CONCLUSIONS: Following previous literature, birth expectations were associated with experiences, and experiences were associated with CB-PTSS. By testing the effect of the match between birth experiences and expectations using an advanced statistical method, we found that experiences play a more substantial role than the match between experiences and expectations in CB-PTSS. The impact of birth experiences on CB-PTSS highlights the importance of respectful and supportive maternity care.

Combined effect of compassionate and uncompassionate self-responding on Chinese college students' mental health during the initial wave of the COVID-19 pandemic: a response surface analysis.

Background: The initial wave of the COVID-19 pandemic significantly deteriorated mental health, especially among college students. Self-compassion has demonstrated benefits for psychological outcomes such as depressive symptoms, life satisfaction, posttraumatic stress symptoms (PTSS), and posttraumatic growth (PTG). Notably, existing literature suggests that the protective and vulnerable aspects within the Self-Compassion Scale, namely, compassionate and uncompassionate self-responding (CSR and USR), can coexist within individuals and influence their mental health through various coexisting patterns. However, this process has not been sufficiently explored.Objective: This study aimed to explore the combined effects of CSR and USR on college students' depressive symptoms, life satisfaction, PTSS, and PTG during the initial wave of the pandemic.Method: In this cross-sectional study, 4450 Chinese college students (51.9% females, Mage = 20.58 years, SD = 1.49) completed self-report measures amid the COVID-19 pandemic's initial wave in 2020. Response surface analyses were utilised to investigate the combined effects of CSR and USR.Results: Simultaneously increased CSR and USR were associated with a slight increase in depressive symptoms, PTSS, and life satisfaction, but a substantial increase in PTG. Conversely, increased CSR and decreased USR were associated with a considerable decrease in depressive symptoms and PTSS, a significant increase in life satisfaction, and a moderate increase in PTG.Conclusions: CSR and USR demonstrated protective and vulnerable impacts, respectively. It is imperative to analyse their combined effects as an interactive system and consider the specific characteristics of different psychological responses.

Increased CSR and decreased USR were associated with less depressive symptoms and PTSS as well as more life satisfaction.CSR mitigated the negative effects of USR on depressive symptoms, life satisfaction, and PTSS.Simultaneously increased CSR and USR were associated with a substantial increase in PTG.

Inconsistency in psychological resilience and social support with mental health in early adolescents: A multilevel response surface analysis approach.

BACKGROUND: Given the high prevalence of adolescent mental health problems, promoting understanding and implementation of protective factors is crucial for prevention and intervention efforts addressing adolescent mental health problems. This study aims to investigate whether consistency and inconsistency in protective factors are associated with adolescent mental health problems and to inform adolescent mental health interventions that target the unique needs of adolescents and promote adolescent mental health. METHODS: We used multistage cluster sampling to conduct psychological resilience, social support, and mental health questionnaires from April to June 2023 among 10,653 Chinese adolescents (52.3 % were boys). Data were analyzed using polynomial regressions with response surface analysis. RESULTS: The higher levels of psychological resilience and social support in adolescents were associated with fewer mental health problems (anxiety: a1 = -1.83, P < 0.001; depression: a1 = -2.44, P < 0.001; and perceived stress: a1 = -1.20, P < 0.001). When the level of psychological resilience was greater than social support, the greater the discrepancy the higher the perceived stress among adolescents (a3 = 1.19, P < 0.001). Moreover, the consistency of psychological resilience and social support had a greater impact on girls' mental health (anxiety: a1 = -1.97, P < 0.001; depression: a1 = -2.71, P < 0.001; perceived stress: a1 = -1.23, P < 0.001). LIMITATIONS: The cross-sectional study design limited the inference of causal relationships between variables. CONCLUSIONS: These results emphasize that adolescents need a balanced development of protective factors and targeted intervention programs for different mental health problems.

The Association between Discrepancies in Parental Emotional Expressivity, Adolescent Loneliness and Depression: A Multi-Informant Study Using Response Surface Analysis.

Incongruent perceptions of parental emotional expressivity between parents and adolescents may signify relational challenges, potentially impacting adolescents' socioemotional adjustment. Direct evidence is still lacking and father-adolescent discrepancies are overlooked. This study employed a multi-informant design to investigate whether both mother-adolescent and father-adolescent discrepancies in perceptions of parental expressivity are related to adolescents' mental well-being, specifically focusing on loneliness and depression. Analyzing data from 681 families (mean age of adolescents = 15.5 years old, 51.2% girls, 40% only-children) in China revealed that adolescents tended to perceive paternal and maternal emotional expressivity more negatively than their parents, particularly fathers. Polynomial regression and response surface analysis showed significant links between parent-adolescent congruence and incongruence and adolescent loneliness. (In)Congruence between adolescents and mothers or fathers predicted later adolescent depression, mediated by adolescent loneliness and varied by the dimension of emotional expressivity. These findings provide insights into the roles of mothers' and fathers' emotional expressivity in shaping children's mental well-being during adolescence.

Discrepancies in perceived family resilience between adolescents with chronic illness and parents: using response surface analysis to examine the relationship with adolescents' psychological adjustment.

BACKGROUND: This study aimed to explore discrepancies in adolescents with chronic illness and their parents' perceptions of family resilience, as well as the relationship between these differences and the psychological adjustment of adolescents with chronic illness. METHODS: A cross-sectional study was conducted. A total of 264 dyads of parents (77.7% mothers, mean age 41.60 years, SD = 6.17) and adolescents (48.5% girls, mean age 12.68 years, SD = 2.11) with chronic illness were recruited through convenience sampling from three children's hospitals in Wenzhou, Hangzhou, and Shanghai, China between June 2022 and May 2023. The Chinese version of the Family Resilience Scale and the Psychological Adjustment Scale, which are commonly used measures with good reliability and validity, were employed to assess family resilience and psychological adaption, respectively. The data were analyzed using polynomial regression and response surface analysis. RESULTS: Adolescents with chronic illness reported higher family resilience than their parents (t=-2.80, p < 0.05). The correlations between family resilience and adolescents' psychological adjustment reported by the adolescents (r = 0.45-0.48) were higher than parents (r = 0.18-0.23). In the line of congruence, there were positive linear (a1 = 1.09-1.60, p < 0.001) and curvilinear (a2=-1.38∼-0.72, p < 0.05) associations between convergent family resilience and adolescents' psychological adjustment. In the line of incongruence, when adolescents reported lower family resilience than parents, adolescents had a lower level of psychological adjustment (a3=-1.02∼-0.45, p < 0.05). Adolescents' sociability decreased when the perceived family resilience of parent-adolescent dyads converged (a4 = 1.36, p < 0.01). CONCLUSION: The findings highlighted the importance of considering the discrepancies and congruence of family resilience in the parent-child dyads when developing interventions to improve the psychological adjustment of adolescents with chronic illness. Interventions aimed at strengthening family communication to foster the convergence of perceptions of family resilience in parent-adolescent dyads were warranted.