Revisiting the Structure and Bonding in Li5H6- and the Exploration of Reactivity: Planar Pentacoordinate Hydrogen.

Recently, Guha and co-workers (Sarmah, K.; Kalita, A.; Purkayastha, S.; Guha, A. K. Pushing The Extreme of Multicentre Bonding: Planar Pentacoordinate Hydride. Angew. Chem. Int. Ed. 2024, e202318741) reported a highly intriguing bonding motif: planar pentacoordinate hydrogen (ppH) in Li5H6-, featuring C2v symmetry in the singlet state with two distinct H-Li (center-ring) bond distances. We herein revisited the potential energy surface of Li5H6- by using a target-oriented genetic algorithm. Our investigation revealed that the lowest-energy structure of Li5H6- exhibits a ppH configuration with very high D5h symmetry and a 1A1' electronic state. We did not find any electronic effect like Jahn-Teller distortion that could be responsible for lowering its symmetry. Moreover, our calculations demonstrated significant differences in the relative energies of other low-lying isomers. An energetically very competitive planar tetracoordinate hydrogen (ptH) isomer is also located, but it corresponds to a very shallow minimum on the potential energy surface depending on the used level of theory. Chemical bonding analyses, including AdNDP and EDA-NOCV, uncover that the optimal Lewis structure for Li5H6- involves H- ions stabilized by the Li5H5 crown. Surprisingly, despite the dominance of electrostatic interactions, the contribution from covalent bonding is also significant between ppH and the Li5H5 moiety, derived from H-(1s) → Li5H5 σ donation. Magnetically induced current density analysis revealed that due to minimal orbital overlap and the highly polar nature of the H-Li covalent interaction, the ppH exhibits local diatropic ring currents around the H centers, which fails to result in a global aromatic ring current. The coordination of Li5H6- with Lewis acids, BH3 and BMe3, instantly converts the ppH configuration to (quasi) ptH. These Lewis acid-bound ptH complexes show high electronic stability and high thermochemical stability against dissociation and, therefore, will be ideal candidates for the experimental realization.

Exploring the Use of "Honorary Transition Metals" To Push the Boundaries of Planar Hypercoordinate Alkaline-Earth Metals.

The quest for planar hypercoordinate atoms (phA) beyond six has predominantly focused on transition metals, with dodecacoordination being the highest reported thus far. Extending this bonding scenario to main-group elements, which typically lack d orbitals despite their larger atomic radius, has posed significant challenges. Intrigued by the potentiality of covalent bonding formation using the d orbitals of the heavier alkaline-earth metals (Ae = Ca, Sr, Ba), the so-called "honorary transition metals", we aim to push the boundaries of planar hypercoordination. By including rings formed by 12-15 atoms of boron-carbon and Ae centers, we propose a design scheme of 180 candidates with a phA. Further systematic screening, structural examination, and stability assessments identified 10 potential clusters with a planar hypercoordinate alkaline-earth metal (phAe) as the lowest-energy form. These unconventional structures embody planar dodeca-, trideca-, tetradeca-, and pentadecacoordinate atoms. Chemical bonding analyses reveal the important role of Ae d orbitals in facilitating covalent interactions between the central Ae atom and the surrounding boron-carbon rings, thereby establishing a new record for coordination numbers in the two-dimensional realm.

New Perspectives on Delocalization Pathways in Aromatic Molecular Chameleons.

This study comprehensively analyzes the magnetically induced current density of polycyclic compounds labeled as "aromatic chameleons" since they can arrange their π-electrons to exhibit aromaticity in both the ground and the lowest triplet state. These compounds comprise benzenoid moieties fused to a central skeleton with 4n π-electrons and traditional magnetic descriptors are biased due to the superposition of local magnetic responses. In the S0 state, our analysis reveals that the molecular constituent fragments preserve their (anti)aromatic features in agreement with two types of resonant structures: one associated with aromatic benzenoids and the other with a central antiaromatic ring. Regarding the T1 state, a global and diatropic ring current is revealed. Our aromaticity study is complemented with advanced electronic and geometric descriptors to consider different aspects of aromaticity, particularly important in the evaluation of excited state aromaticity. Remarkably, these descriptors consistently align with the general features on the main delocalization pathways in polycyclic hydrocarbons consisting of fused 4n π-electron rings. Moreover, our study demonstrates an inverse correlation between the singlet-triplet energy difference and the antiaromatic character of the central ring in S0.

Update for Isomerization Stabilization Energies: The Fulvenization Approach.

An alternative approach for calculating aromatic stabilization energies is proposed based on transforming an (anti)aromatic ring into a fulvene isomer. This fulvenization process gives a value of 34.05 kcal·mol-1 for benzene in the singlet state and a value of -17.85 kcal·mol-1 in the triplet state. Additionally, it is possible to use experimental values (as long as they exist) for the calculation as the gas-phase formation enthalpies of benzene and fulvene, whose difference is 33.72 kcal·mol-1. On the other hand, this same approach has been evaluated on several six-membered rings, including those persubstituted, biradicals, azines, and inorganic analogues, giving results in agreement with those reported in the literature using different criteria. Additionally, it is possible to differentiate the aromaticity of the rings in polycyclic aromatic hydrocarbons according to Clar's rules. Assigning the (anti)aromatic character in various nonbenzenoid rings (neutral and charged), except for five- and seven-membered rings, is also possible. The construction of the fulvene isomers in PAHs is set such that nonaromaticity-related effects are not considered. The results show that the fulvenization approach is an effective and efficient approach that can serve as an alternative or complement to existing tools.

Effectiveness of non-surgical management in rotator cuff calcific tendinopathy (the effect trial): protocol for a randomised clinical trial.

INTRODUCTION: Rotator cuff calcific tendinopathy (RCCT) involves calcific deposits in the rotator cuff. Non-surgical interventions such as extracorporeal shockwave therapy (ESWT) and ultrasound-guided percutaneous irrigation of calcific tendinopathy (US-PICT) are recommended for its early management. Exercise therapy (ET) has shown to be an effective intervention for people with rotator cuff tendinopathy, but it has not been formally tested in RCCT. The main objective of this study is to compare the effectiveness of an ET programme with ESWT and US-PICT in people with RCCT. As a secondary aim, this study aims to describe the natural history of RCCT. METHODS AND ANALYSIS: A randomised, single-blinded four-group clinical trial will be conducted. Adults from 30 to 75 years diagnosed with RCCT who accomplish eligibility criteria will be recruited. Participants (n=116) will be randomised into four groups: ET group will receive a 12-week rehabilitation programme; ESWT group will receive four sessions with 1 week rest between sessions during 1 month; US-PICT group will receive two sessions with 3 months of rest between sessions; and (actual) wait-and-see group will not receive any intervention during the 12-month follow-up. The primary outcome will be shoulder pain assessed with the Shoulder Pain and Disability Index at baseline, 2 weeks, 4 months, 6 months and 12 months from baseline. The primary analysis will be performed at 12 months from baseline. Secondary outcomes will include pain, range of motion, patient satisfaction and imaging-related variables. Moreover, the following psychosocial questionnaires with their corresponding outcome measure will be assessed: Central Sensitization Inventory (symptoms related to central sensitization); Pain Catastrophizing Scale (pain catastrophizing); Tampa Scale for Kinesiophobia 11 items (fear of movement); Fear Avoidance Belief Questionnaire (fear avoidance behaviour); Hospital Anxiety and Depression Scale (anxiety and depression); Pittsburgh Sleep Quality Index (sleep quality); and the EuroQol-5D (quality of life). An intention-to-treat analysis will be performed to reduce the risk of bias using a worst-case and best-case scenario analysis. ETHICS AND DISSEMINATION: Ethics committee approval for this study has been obtained (reference number: 1718862). The results of the main trial will be submitted for publication in a peer-reviewed journal. TRIAL REGISTRATION NUMBER: NCT05478902.

Li6 E5 Li6 : Tetrel Sandwich Complexes with 10-π-Electrons.

When (4n +2) π-electrons are located in single planar ring, it conventionally qualifies as aromatic. According Hückel's rule, systems possessing ten π-electrons should be aromatic. Herein we report a series of D5h  Li6 E5 Li6 sandwich structures, representing the first global minima featuring ten π-electrons E5 10- ring (E=Si-Pb). However, these π-electrons localize as five π-lone-pairs rather than delocalized orbitals. The high symmetry structure achieved is a direct consequence of σ-aromaticity, particularly favored in elements from Si to Pb, resulting in a pronounced diatropic ring current flow that contributes to the enhanced stability of these systems.

Aromaticity and Magnetic Behavior in Benzenoids: Unraveling Ring Current Combinations.

Nowadays, an active research topic is the connection between Clar's rule, aromaticity, and magnetic properties of polycyclic benzenoid hydrocarbons. In the present work, we employ a meticulous magnetically induced current density analysis to define the net current flowing through any cyclic circuit, connecting it to aromaticity based on the ring current concept. Our investigation reveals that the analyzed polycyclic systems display a prominent global ring current, contrasting with subdued semi-local and local ring currents. These patterns align with Clar's aromatic π-sextets only in cases where migrating π-sextet structures are invoked. The results of this study will enrich our comprehension of aromaticity and magnetic behavior in such systems, offering significant insights into coexisting ring current circuits in these systems.

Recruitment and Feasibility of Hair Cortisol Collection in a Sample of Ethnically and Sexually Diverse, Low-Income Adults: A Qualitative Community-Partnered Participatory Research Study.

The current study describes how a community-partnered participatory research (CPPR) model was used to enhance hair cortisol research engagement among low-income adults of diverse ethnicities and sexual and gender identities. Participants' reported motivations and concerns surrounding providing a hair sample are also described. Participants from a larger longitudinal study were invited to provide a hair sample and/or complete acceptability interviews. Results indicated that 71% of all persons (N=133) contacted participated in the current study, of whom 82% provided hair samples. Several themes emerged from the interviews indicating that participants were motivated to provide a hair sample due to internal and external factors; however, concerns about mistrust of research remained. Thus, collecting biospecimens in research with underserved groups requires careful consideration of benefits and risks to the individual and their communities. Our results provide guidelines for engaging low-income racially/ethnically and sexually diverse community members in biospecimen research to understand stress-health relationships.

Revisiting the potential-energy surface of CnBe3n+2H2n+22+ (n = 2-4) clusters: are planar pentacoordinate carbon structures the global minima?

Using various exploration strategies, in this study, we investigated the potential energy surfaces (PES) of CBe5H5+ and CnBe3n+2H2n+22+ (n = 2-4) clusters. Previous studies proposed that the planar pentacoordinate carbons (ppCs) were the global minima of these clusters. However, our study identified new putative global minima and competitive isomers, refuting some previous assignments. We employed several methods, including evolutive-inspired stochastic approaches guided by "chemical criteria", and ab initio molecular dynamics simulations at elevated temperatures. Our results showed that the size of the scanned population significantly affected the evolutive method and that constrained or guided procedures showed an advantage in identifying better minima for larger systems. This study demonstrated that using multiple complementary strategies can result in a wider variety of minima in a given energy range. Our findings provide valuable insights into exploring the potential energy surfaces of clusters, mainly medium-sized clusters, which could be the connections between small clusters and nanomaterials.

B7 Be6 B7 : A Boron-Beryllium Sandwich Complex.

Planar boron clusters have often been regarded as "π-analogous" to aromatic arenes because of their similar delocalized π-bonding. However, unlike arenes such as C5 H5 - and C6 H6 , boron clusters have not previously shown the ability to form sandwich complexes. In this study, we present the first sandwich complex involving beryllium and boron, B7 Be6 B7 . The global minimum of this combination adopts a unique architecture having a D6h geometry, featuring an unprecedented monocyclic Be6 ring sandwiched between two quasi-planar B7 motifs. The thermochemical and kinetic stability of B7 Be6 B7 can be attributed to strong electrostatic and covalent interactions between the fragments. Chemical bonding analysis shows that B7 Be6 B7 can be considered as a [B7 ]3- [Be6 ]6+ [B7 ]3- complex. Moreover, there is a significant electron delocalization within this cluster, supported by the local diatropic contributions of the B7 and Be6 fragments.

"I Don't Feel at Home in This World" Sexual and Gender Minority Emerging Adults' Self-Perceived Links Between Their Suicidal Thoughts and Sexual Orientation or Gender Identity.

OBJECTIVES: To examine whether sexual and gender minority (SGM) emerging adults perceived their SGM status was linked to suicidal ideation, and to explore if their responses fell within tenets of the minority stress framework. METHOD: Open text (survey) responses of Dutch and Flemish SGM emerging adults (n = 187) were thematically analysed using the constant comparative comparison method for qualitative analysis. RESULTS: We identified 8 themes in our qualitative analysis. Two themes fell within the scope of the minority stress framework that has received little attention: (1) concerns about relationships and family planning and (2) feeling different (internal stressor). Two additional themes emerged largely beyond the scope of existing minority stress framework studies on suicidality: (3) SGM-related questioning; (4) negativity in LGBT communities. Four established minority stress framework themes emerged: (5) gender identity stress; (6) victimization; (7) coming-out stress; (8) psychological difficulties linked to SGM status. CONCLUSION: Suicide prevention needs to focus on supporting SGM emerging adults who worry about feeling "different", or who have concerns over their romantic and family life, on reducing gender minority stress, as well as on caring for those who are victimized due to their sexual or gender identity.

COVID-19-Related Household Job Loss and Mental Health in a Nationwide United States Sample of Sexual Minority Adolescents.

Household job loss during COVID-19 constitutes a public health crisis. Research suggests associations between household job loss, harsher parenting practices, and mental health challenges in the general population. Sexual minority adolescents (SMA) face high rates of family stress and rejection, but evidence linking household job loss to SMA mental health is lacking. This study evaluated associations between household job loss, family rejection, and mental health with a national sample of SMA who were sheltering in place with families during the pandemic. SMA from an ongoing prospective study completed an online questionnaire between May 13-31, 2020. It was hypothesized that household job loss during the pandemic would be associated with elevated depressive and anxiety symptoms through family rejection. Household job loss during the pandemic was indirectly associated with SMA mental health through family rejection. These findings highlight how socioeconomic change and policy carry implications for SMA health.

Greater lifetime stressor exposure is associated with poorer mental health among sexual minority people of color.

BACKGROUND: Research has shown that sexual minority people of color experience pervasive and sometimes severe life stressors that increase their risk of experiencing mental health problems, and that can contribute to lifelong health disparities. However, no studies in this population have investigated stressor exposure occurring over the entire lifespan. Moreover, it remains unknown whether these stressor-health effects differ based on the timing or types of stressors experienced. PURPOSE: The purpose of this study is to examine how cumulative lifetime stressor exposure is associated with mental health among Black, Latinx, and biracial Black-Latinx sexual minority persons. METHOD: Participants were 285 ethnic/racial minority young adults (Mage = 25.18 years old, SD = 1.94, age range = 19-29 years), who completed the Stress and Adversity Inventory for Adults to assess for retrospective reports of lifetime stressor count and severity. The Brief Symptom Inventory was used to assess participants' symptoms of anxiety, depression, and somatization, which were the main outcomes. Most participants identified as cisgender male (94.7%) and gay (74.2%), with the remaining participants identifying as transgender or genderqueer/nonbinary for gender and bisexual/pansexual, queer, or another sexual orientation. RESULTS: Multiple regression analyses indicated that experiencing more-and more severe-stressors across the lifespan was related to greater anxiety, depressive, and somatization symptoms. These effects were robust while controlling for race/ethnicity, sexual orientation, education, and employment status, and they differed based on stressor exposure timing, type, primary life domain, and core social-psychological characteristic. CONCLUSION: Greater cumulative lifetime stressor exposure is related to poorer mental health among sexual minority people of color. Screening for lifetime stressors may thus help identify at-risk persons and provide an opportunity to intervene to help mitigate or prevent mental health disparities in multiply stigmatized adults.

Explaining behavioral health differences in urban and rural sexual minority adolescents: A longitudinal investigation of minority stress in a diverse national sample of sexual minority adolescents: A longitudinal investigation of minority stress in a diverse national sample of sexual minority adolescents.

PURPOSE: Experiences of sexuality-based discrimination (ie, minority stressors) against youth who identify as nonheterosexual (ie, sexual minority) have been associated with increased symptoms of anxiety, depression, and post-traumatic stress disorder (PTSD) for sexual minority adolescents (SMA; ages 14-17). However, little is known about the experiences of SMA living in rural communities across the United States. Thus, the present study sought to examine differences in mental health patterns between urban and rural dwelling SMA, and to see whether these differences are, at least in part, explained by experiences of lifetime minority stress. METHODS: A nationwide sample of SMA residing in the United States (N = 2,558; aged 14-17, M = 15.90 years, SD = 0.98) was recruited through purposive social media and respondent-driven sampling methods to complete a cross-sectional survey online. Measures included those of minority stress, urbanicity, and symptoms of anxiety, depression, and PTSD. Parallel multiple mediation (PMM) analysis was employed to test whether urbanicity was associated with anxiety, depressive, and PTSD symptoms through reported lifetime minority stress. FINDINGS: On average, SMA living in rural areas significantly reported more lifetime minority stress, depressive, and PTSD symptoms than SMA living in urban settings. Results from our PMM analysis indicated that heightened experiences of lifetime minority stress indirectly linked the effects of living in rural areas on anxiety (b = -0.288, 95% CI = [-0.491, -0.085]), depressive (b = -0.158, 95% CI = [-0.270, -0.047), and PTSD symptoms PTSD (b = -0.349, 95% CI = [-0.596, -0.105]). The model accounted for 16.8%, 18%, and 24.1% of the variability in anxiety symptoms, depressive symptoms, and PTSD symptoms, respectively. CONCLUSIONS: SMA in our study who reside in rural areas reported elevated minority stress, depressive, and PTSD symptoms as compared to their urban dwelling peers. Our study found that lifetime experiences of minority stress fully mediated the relationship between urbanicity and both depressive and PTSD symptoms, and partially mediated the relationship between urbanicity and anxiety. These findings highlight the need to increase support for rural youth who are growing into adulthood and may find continuing challenges in their family, peer, and community relationships.

E6C15 (E = Si-Pb): polycyclic aromatic compounds with three planar tetracoordinate carbons.

A systematic exploration of the potential energy surface reveals two global minima with three planar tetra coordinate carbons (ptCs) and two global minima with three quasi-ptCs for E6C15 (E = Si-Pb) combinations. These consist of aromatic polycyclic templates suitable for further design of different materials without hindering the ptC texture.

Bowl-shaped Cluster CuB12 - : A Viable Global Minimum with Twofold Aromaticity.

A low-lying structure is revealed for the CuB12 - cluster, which is bowl-shaped. It consists of a triangular CuB2 base and a B10 rim. Molecular dynamics simulations indicates its structural robustness; at an elevated temperature (600 K), the base rotates reversibly within the B10 perimeter. Chemical bonding analysis detects 2σ- and 3π-delocalized bonds, suggesting double aromaticity. This is also confirmed by two diatropic and concentric ring currents under an external magnetic field.

Agaricus macrochlamys, a New Species from the (Sub)tropical Cloud Forests of North America and the Caribbean, and Agaricus fiardii, a New Synonym of Agaricus subrufescens.

Agaricus is a genus of fungi in the family Agaricaceae, with several highly priced edible and medicinal species. Here we describe Agaricus macrochlamys, a new species, in A. sect. Arvenses, sympatric and morphologically cryptic with the edible and medicinally cultivated mushroom, A. subrufescens. Phylogenetic analyses showed that A. macrochlamys is closely related to A. subrufescens, and that A. fiardii is a new synonym of A. subrufescens. Despite being morphologically cryptic, A. macrochlamys can be distinguished from A. subrufescens by several ITS and tef1α species-specific markers and a 4-bp insertion in the tef1α sequence. Furthermore, A. subrufescens is a cosmopolitan species, while A. macrochlamys distribution is so far restricted to Mexico, the Dominican Republic, and the United States.

Adrenocortical responses of emerging adults in California in the two months following the Pulse night club massacre: Evidence for distal stress responses.

This study examined adrenocortical responses in the days following the Pulse nightclub massacre on June 12, 2016, among emerging adults in Northern California (N = 202; M = 23.18 years, SD = 2.56; 25% LGBQ-Latinx, 25% LGBQ-White, 25% Straight-Latinx, and 25% Straight-White) between June 13-August 12, 2016. As predicted, participants tested more proximally to the massacre had higher waking cortisol (intercepts) and flatter diurnal cortisol output (slopes), indicative of time-dependent adrenocortical arousal across the day. The effect of days post-massacre on waking cortisol was moderated by daily distress, with days since the Pulse massacre predicting waking cortisol significant only for participants reporting lower distress; participants who reported feeling higher daily distress had elevated waking cortisol across the testing period. These findings were independent of weekly personal stressors, and consistent across participants' demographic and identity characteristics. The violent attack at the Pulse nightclub was connected to increased waking cortisol and diurnal cortisol production for several days after the massacre, in a distal population exposed to the massacre vicariously, and especially for individuals not experiencing other, personal stressors. Heightened physiological responses to violent crimes support policy efforts to protect vulnerable communities, including violence prevention, gun control, and community-based trauma response services for those directly and indirectly affected by gun violence.

Access to health services among sexual minority people in the United States.

Sexual minority people in the United States are less likely to have access to health services when compared to their heterosexual counterparts. Less is known about the within-group sociodemographic memberships among sexual minority people regarding access to health services. Using data from a nationally representative sample, a series of univariate and bivariate analyses were used to determine associations between sociodemographic group membership and access to health services. Results suggest there are significant differences in access to health services within the sexual minority population. Differences in access to health services when considering sex-at-birth, sexual identity, age, race/ethnicity, urbanicity, education level and income status were found. These findings offer insight into the role sociodemographic group membership has on the equity of access to health services. Specifically, results indicated that disproportionate access to health services among sexual minority people were more pronounced among those with group membership who experience social marginalisation. This was particularly true for sexual minority people who were bisexual, younger, Black and Latinx, lower-income earners and sexual minority people with less education attainment. Results from this study may be used to inform policies and practices aimed at improving access to health services including, but not limited to, the expansion of the Affordable Care Act and continued development of Federally Qualified Health Centers, while acknowledging the role of within-group differences among sexual minority people.

Conceptualizing the Influence of Social and Structural Determinants of Neurobiology and Mental Health: Why and How Biological Psychiatry Can Do Better at Addressing the Consequences of Inequity.

Psychiatry and allied disciplines have recognized the potency of structural and social determinants of mental health, yet there has been scant attention given to the roles of neurobiology in the links between structural and social determinants and mental health. In this article, we make the case for why greater attention must be given to structural and social determinants of biological psychiatry by researchers, practitioners, and policy-makers. After defining these terms and theoretical frameworks for considering their relevance in biological psychiatry, we review empirical research with marginalized and minoritized racial, ethnic, gender, sexual, and economic communities that reveals the ways in which structural and social determinants affect neurobiological functioning with implications for mental health. We give particular emphasis to developmental science and developmentally informed research, because structural and social determinants influence neurobiological adaptation and maturation across the lifespan. We conclude with recommendations for advancing research, practice, and policy that connect biological psychiatry with structural and social determinants of health. Foremost among these is diversifying the ranks of biological psychiatry, from classrooms through laboratories, hospitals, and community health centers. Transforming and advancing the understanding of the structural and social determinants of neurobiology and mental health is most likely to come through transforming the discipline itself.