Early stages of covalent organic framework formation imaged in operando.

Covalent organic frameworks (COFs) are a functional material class able to harness, convert and store energy. However, after almost 20 years of research, there are no coherent prediction rules for their synthesis conditions. This is partly because of an incomplete picture of nucleation and growth at the early stages of formation. Here we use the optical technique interferometric scattering microscopy (iSCAT)1-3 for in operando studies of COF polymerization and framework formation. We observe liquid-liquid phase separation, pointing to the existence of structured solvents in the form of surfactant-free (micro)emulsions in conventional COF synthesis. Our findings show that the role of solvents extends beyond solubility to being kinetic modulators by compartmentation of reactants and catalyst. Taking advantage of these observations, we develop a synthesis protocol for COFs using room temperature instead of elevated temperatures. This work connects framework synthesis with liquid phase diagrams and thereby enables an active design of the reaction environment, emphasizing that visualization of chemical reactions by means of light-scattering-based techniques can be a powerful approach for advancing rational materials synthesis.

Regioisomerism in Thienothiophene-Based Covalent Organic Frameworks─A Tool for Band-Gap Engineering.

The craft of tuning optical properties is well-established for crystalline inorganic and hybrid solids. However, a far greater challenge is to tune the optical properties of organic materials systematically by design. We now introduce a synthesis concept that enables us to alter the optical properties of crystalline covalent organic frameworks (COFs) systematically using isomeric structures of thienothiophene-based building blocks (T23/32T) combined with a variety of tetratopic aromatic amines, e.g., the Wurster moiety (W-NH2). This concept is demonstrated for the synthesis of COFs in bulk and film forms and provides highly crystalline and porous isomeric COFs featuring predesigned photophysical properties. The band gap of the framework can be tuned continuously and precisely by chemically doping the pristine W23TT COF with its related constitutional isomer building block. Density-functional theory investigations of COF model compounds indicate that the extent of π-conjugation is among the key characteristics enabling the band-gap engineering.

Tunable Isometric Donor-Acceptor Wurster-Type Covalent Organic Framework Photocathodes.

Covalent organic frameworks (COFs) offer remarkable versatility, combining ordered structures, high porosity, and tailorable functionalities in nanoscale reaction spaces. Herein, we report the synthesis of a series of isostructural, photoactive Wurster-type COFs achieved by manipulating the chemical and electronic nature of the Wurster aromatic amine building blocks. A series of donor-acceptor-donor (D-A-D) Wurster building block molecules was synthesized by incorporating heteroaromatic acceptors with varying strengths between triphenylamine donor groups. These tailored building blocks were integrated into a 2D COF scaffold, resulting in highly crystalline structures and similar morphologies across all COFs. Remarkably, this structural uniformity was also achieved in the synthesis of homogeneous and oriented thin films. Steady-state photoluminescence revealed a tunable red-shift in film emission exceeding 100 nm, demonstrating effective manipulation of their optical properties. Furthermore, photoelectrochemical studies exhibited a doubled current density (8.1 µA cm-2 at 0.2 VRHE) for the COF with the strongest acceptor unit. These findings highlight the potential of these D-A-D COFs in photoelectrochemical water splitting devices and pave the way for further exploration of structure-property relationships in this promising class of photoactive materials.

Mammalian VPS45 orchestrates trafficking through the endosomal system.

Vacuolar protein sorting 45 homolog (VPS45), a member of the Sec1/Munc18 (SM) family, has been implicated in the regulation of endosomal trafficking. VPS45 deficiency in human patients results in congenital neutropenia, bone marrow fibrosis, and extramedullary renal hematopoiesis. Detailed mechanisms of the VPS45 function are unknown. Here, we show an essential role of mammalian VPS45 in maintaining the intracellular organization of endolysosomal vesicles and promoting recycling of cell-surface receptors. Loss of VPS45 causes defective Rab5-to-Rab7 conversion resulting in trapping of cargos in early endosomes and impaired delivery to lysosomes. In this context, we demonstrate aberrant trafficking of the granulocyte colony-stimulating factor receptor in the absence of VPS45. Furthermore, we find that lack of VPS45 in mice is not compatible with embryonic development. Thus, we identify mammalian VPS45 as a critical regulator of trafficking through the endosomal system and early embryogenesis of mice.

Unpacking the Meaning of Closeness, Reconsidering the Concept of Impact in Suicide Exposure, and Expanding Beyond Bereavement: "Just, I Hope You Don't Forget About Us".

Suicide exposure research has relied on samples of treatment-seeking kin, resulting in an attachment-based model centering bereavement as the most significant form of impact and obscuring other forms of significant and life-altering impact. From a community-based sample (N = 3010) exposed to suicide, we examine a subset (n = 104) with perceived high impact from the death yet low reported closeness to the person who died and analyze qualitative comments (n = 50). On average and out of 5.00, participants rated closeness as 1.56 but impact of death as 4.51. We illustrate dimensions of low closeness and identify themes on the meaning of impact: impact through society and systemic circumstances, impact through history and repeated exposure, impact through other people, impact as a motivator for reflection or change, and impact through shared resonance. Participants reported impact of death as significant or devastating, yet none of their comments reflected experiences typical of bereavement.

Building Blocks and COFs Formed in Concert-Three-Component Synthesis of Pyrene-Fused Azaacene Covalent Organic Framework in the Bulk and as Films.

A three-component synthesis methodology is described for the formation of covalent organic frameworks (COFs) containing extended aromatics. Notably, this approach enables synthesis of the building blocks and COF along parallel reaction landscapes, on a similar timeframe. The use of fragmental building block components, namely pyrene dione diboronic acid as aggregation-inducing COF precursor and the diamines o-phenylenediamine (Ph), 2,3-diaminonaphthalene (Naph), or (1R,2R)-(+)-1,2-diphenylethylenediamine (2Ph) as extending functionalization units in conjunction with 2,3,6,7,10,11-hexahydroxytriphenylene, resulted in the formation of the corresponding pyrene-fused azaacene, i.e., Aza-COF series with full conversion of the dione moiety, long-range order, and high surface area. In addition, the novel three-component synthesis was successfully applied to produce highly crystalline, oriented thin films of the Aza-COFs with nanostructured surfaces on various substrates. The Aza-COFs exhibit light absorption maxima in the blue spectral region, and each Aza-COF presents a distinct photoluminescence profile. Transient absorption measurements of Aza-Ph- and Aza-Naph-COFs suggest ultrafast relaxation dynamics of excited-states within these COFs.

What's in a word? Clarifying terminology on suicide-related communication.

Efforts to clarify suicide terminology fail to address nuances in suicide-related communication, often relying on poorly-defined terms or implying communication exists primarily as manipulation. In the present paper, we review examples from existing literature and explore how personal suicide-related communication differs from prevention and exposure communication. We also separate definitions for five common types of personal-suicide-related communication: (a) suicide-related disclosure, (b) suicide-related notification, (c) unintended suicide-related communication, (d) coerced suicide-related communication, and (e) conditional suicide-related communication. Finally, we provide specific ways in which standardized definitions can enhance both research and clinical efforts in the future.

Are the "Right" People Selected for First Disclosures About Suicidal Thoughts? Exploring What We Know About Advance Care Planning in the Context of Safety Planning.

Nominating primary confidants (i.e., safety plan nominees) is central to safety planning for suicide but there is a dearth of research about such confidants-a serious oversight given their high-leverage position to affect pathways into clinical care. Informed by advance care planning (ACP) work, this study examined differences between social network members who were and were not identified as primary confidants on attributes that could impact their effectiveness in a helping role. Using social network methodology, information was collected from 41 individuals with affective disorders about the 332 people and relationships in their networks. Logistic regression analysis revealed that being perceived as capable of managing stress and prioritizing the participant's best interests over one's own increased the odds of being a primary confidant. Clinicians working with suicidal individuals may benefit from integrating ACP principles-which recognize the thoughtful selection of nominees based on specific attributes-into their safety planning procedures.

Exploring suicide-related disclosure motivation and the impact on mechanisms linked to suicide.

Suicide-related disclosure enables improved risk management but disclosure motivations are understudied. This study identified reasons for and against disclosing suicidal thoughts and examined their link to future disclosure and interpersonal needs among 44 people receiving psychiatric care. The most endorsed reasons for disclosure (approach-motivations) included help-seeking, shared background, and catharsis. The most endorsed reasons against disclosure (avoidance-motivations) included fear of rejection, shame, and hospitalization. Higher mean approach motivation was associated with more disclosure intent and less burdensomeness. No associations with avoidance motivation were observed. Programming that seeks to orient people toward approach motivation holds promise for attenuating suicide risk.

A Dual-layered Microfluidic System for Long-term Controlled In Situ Delivery of Multiple Anti-inflammatory Factors for Chronic Neural Applications.

We report the development of a microfluidic system capable of repeated infusions of anti-inflammatory factors post-implantation for use as a coating for neural probes. This system consists of a microchannel in a thin gelatin methacryloyl (GelMA)-polyethylene glycol (PEG) composite hydrogel surrounded by a porous polydimethylsiloxane (PDMS) membrane, where the hydrogel can be dried to increase the stiffness for easy insertion. Reswelling allowed us to perfuse interleukin (IL)-4 and dexamethasone (DEX) as anti-inflammatory factors through the channel with minimal burst release and significant amounts of IL-4 were observed to release for up to 96 hr post-infusion. Repeated injections of IL-4 increased the ratio of prohealing M2 versus proinflammatory M1 phenotypes of macrophages encapsulated in the hydrogel by six fold compared with a single injection, over a 2-week period. These repeated infusions also significantly downregulated the expression of inflammatory markers tumor necrosis factor (TNF)-α and IL-6 in astrocytes encapsulated in hydrogel. To demonstrate the system as a coating of neural probe for in vivo applications, we further fabricated a prototype device, where a thin dual-layered microfluidic system was integrated onto a metal probe. Such a drug delivery system could help reduce the formation of a glial scar around neural probes.

Talking about suicide may not be enough: family reaction as a mediator between disclosure and interpersonal needs.

BACKGROUND: Although most people who make an attempt do not die, attempt survivors remain at particularly elevated risk for suicide in the short- and long-term. Moreover, the research on suicide-related disclosure and subsequent family reactions on risk factors for the development of suicidal desire is limited. AIMS: This study examined the relationships between disclosure, family reaction and two interpersonal needs connected to the development of suicidal desire. METHODS: Data from 74 attempt survivors who participated in a larger study were analyzed to assess the relationships between degree of suicide-related disclosure, quality of family reaction and thwarted belongingness and perceived burdensomeness. RESULTS: Results indicated that higher rates of disclosure predicted more positive family reactions, which in turn predicted lower levels of thwarted belongingness and perceived burdensomeness. Although there was no direct relationship between disclosure and the outcome variables, bootstrapping analyses indicated that family reaction mediated the relationship between disclosure and both belongingness and burdensomeness. CONCLUSIONS: These findings suggest the need for more family interventions that promote healthy reactions following suicide-related disclosure in order to facilitate the recovery and treatment process.

An electrically conducting 3D coronene-based metal-organic framework.

A novel cubic mesoporous metal-organic framework (MOF), consisting of hexahydroxy-cata-hexabenzocoronene (c-HBC) and FeIII ions is presented. The highly crystalline and porous MOF features broad optical absorption over the whole visible and near infrared spectral regions. An electrical conductivity of 10-4 S cm-1 was measured on a pressed pellet.

A safe bet? Transgender and gender diverse experiences with inclusive therapists.

Historically, the global mental health system has pathologized transgender and gender diverse (TGD) identities, imposing spurious diagnoses and nocuous "cures." Recently, the World Health Organization declassified "transgender" as a mental health disorder, and psychological organizations have acknowledged the harmful practice of conversion therapy and other culturally inept interventions. Some practitioners have begun to advertise their therapeutic services as "trans-affirming" or "trans-competent," but to date, there are no published studies delineating their efficacy. The following content analysis addresses this gap by considering the open-ended responses of 1,567 participants in the Trans Mental Health Survey. While inclusive mental health care is clearly needed, this study suggests that affirming providers are not axiomatically adroit: some providers inflate their expertise, conflate TGD experiences with sexual minority experiences, and manipulate their clients. Conversely, competent providers are identified by their helpfulness, trustworthiness, and understanding of TGD issues. In addition to promulgating best practices, this content analysis also acknowledges systemic barriers to quality care. The solutions to these macroissues include free or affordable mental health care and increased access to services. (PsycInfo Database Record (c) 2022 APA, all rights reserved).

Review of family-based treatments from 2010 to 2019 for suicidal ideation and behavior.

Suicide ideation and behavior are pervasive public health issues. Given that positive interpersonal relationships can be a protective factor against suicide risk, we conducted a systematic review to examine peer-reviewed publications from 2010 to 2019 that included empirical data, tested an intervention with at least some family component, and included a suicide-related outcome measure. We reviewed and synthesized findings from 22 articles covering 7 intervention categories with 12 interventions to examine the treatment components and the quality of evidence to support them. Using Southam-Gerow and Prinstein's (Child Adolesc Psychol 43:16, 2014) guidelines, we identified two well-established intervention categories that met the highest standards for interventions and three probably efficacious intervention categories. All interventions found focused solely on suicide risk in adolescent populations. More studies are needed for adult populations and to explore the role of family moderators and mediators to test whether suicide outcomes are reduced by improvement in the family environment.

Public Health Surveillance of Youth Suicide Attempts: Challenges and Opportunities.

BACKGROUND: Surveillance of youth suicide attempts presents many challenges. To assess common data sources that capture information about youth suicidal behavior, we compared counts of high school students who reported (a) a suicide attempt and (b) an injurious suicide attempt, requiring medical treatment in the previous twelve months, with counts of suicide deaths and intentional self-injuries obtained from administrative data sources. METHOD: Youth Risk Behavior Surveillance System (YRBSS), high school enrollments, and vital statistics were used to estimate the ratio of suicide attempts to suicide deaths among Kentucky high school students. YRBSS and enrollment data were used to estimate the number of Kentucky high school students who received medical treatment following a suicide attempt, which was compared with hospital and emergency department (ED) discharges for intentional self-injury from administrative claim records. RESULTS: We estimated 943 students reporting a suicide attempt for every suicide death, a result that is higher than previous estimates for youth. Self-reported suicide attempts resulting in medical treatment were 7.5 times higher than self-injuries reported in claims records. CONCLUSION: Future research should address concerns about undocumented cases of intentional self-injury in administrative claims systems; patient encounters in nonhospital settings for injuries resulting from a suicide attempt; and validity of Youth Risk Behavior Survey questions on suicidal behavior.

"Nobody Hears a Silent Cry for Help": Suicide Attempt Survivors' Experiences of Disclosing During and After a Crisis.

Suicide remains an important public health issue across the globe. Until recently the medically dominated field of suicide prevention has neglected first-hand accounts of suicidal thoughts and behaviors from those who have survived prior suicide attempts. This qualitative research provides insight into the experience of suicide attempt, highlighting difficulties with disclosure of suicidal thinking prior to, and after, suicide attempts. Semi-structured interviews were undertaken with 31 adult suicide attempt survivors. The focus of the interviews was to explore their experience of suicide attempt and recovery. This paper reports on the complexity involved in disclosing suicidal thoughts or behavior prior to, at the time, or post attempt; the role that help seeking has when someone is acutely suicidal; and the challenges people have in finding their voice at these critical junctures. These factors are both inter- and intra-personal, and are influenced by stigma and lack of understanding of the suicidal state.

Anticipated Suicide Stigma, Secrecy, and Suicidality among Suicide Attempt Survivors.

OBJECTIVE: Suicidal behavior is stigmatized, and suicide attempt survivors often keep their experiences secret. Although secrecy can protect from discrimination, research from related fields suggests that both the experience of stigma and secrecy can contribute to suicidality. Although suicide attempt survivors are at high risk for reattempt, research investigating the link between suicide stigma and suicidality among this group is rare. METHOD: A community sample of 159 suicide attempt survivors participated in an online survey in the US. We used multiple linear regression models to test the association between anticipated suicide stigma and current suicidality, as well as a path model to test the mediating effect of secrecy. RESULTS: After controlling for age, sex, number of lifetime suicide attempts, and time since the most recent suicide attempt, anticipated suicide stigma was significantly associated with increased suicidality. In a controlled path model, this link was partially mediated by increased secrecy. CONCLUSION: These results provide initial support that anticipated suicide stigma, and secrecy can contribute to suicidality among suicide attempt survivors. Therefore, programs to support suicide attempt survivors in coping with suicide stigma and secrecy, as well as interventions to reduce harmful aspects of public suicide stigma, could contribute to suicide prevention.

Author Correction: Human FCHO1 deficiency reveals role for clathrin-mediated endocytosis in development and function of T cells.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Human FCHO1 deficiency reveals role for clathrin-mediated endocytosis in development and function of T cells.

Clathrin-mediated endocytosis (CME) is critical for internalisation of molecules across cell membranes. The FCH domain only 1 (FCHO1) protein is key molecule involved in the early stages of CME formation. The consequences of mutations in FCHO1 in humans were unknown. We identify ten unrelated patients with variable T and B cell lymphopenia, who are homozygous for six distinct mutations in FCHO1. We demonstrate that these mutations either lead to mislocalisation of the protein or prevent its interaction with binding partners. Live-cell imaging of cells expressing mutant variants of FCHO1 provide evidence of impaired formation of clathrin coated pits (CCP). Patient T cells are unresponsive to T cell receptor (TCR) triggering. Internalisation of the TCR receptor is severely perturbed in FCHO1-deficient Jurkat T cells but can be rescued by expression of wild-type FCHO1. Thus, we discovered a previously unrecognised critical role of FCHO1 and CME during T-cell development and function in humans.

Suicidal Ideation and Behavior Among Youth Victims of Sex Trafficking in Kentuckiana.

Background: Youth experiencing homelessness are at risk for sex trafficking and mental health concerns. Aims: More information is needed to elucidate the prevalence and characteristics of suicidal ideation and behavior among youth experiencing sex trafficking. Method: The present study examined suicidal ideation and behavior in a convenience sample of 128 youths experiencing homelessness aged 12-25 years in metropolitan Louisville, Kentucky, and southern Indiana. Participants were asked seven questions regarding suicidal ideation and attempts as part of an enhanced version of the 60-item Youth Experiences Survey (YES). Results: Approximately 53% of the sample reported experiencing suicidal ideation at some point in their lifetime and the odds of a youth experiencing homelessness who had experienced sex trafficking reporting suicidal ideation was 3.87 times higher than the odds of a youth experiencing homelessness who had not experienced sex trafficking. Additionally, of those who reported experiencing suicidal ideation, the majority (84.4%) reported they had attempted suicide in their lifetime. Limitations: This study relied on a convenience sample of youth receiving services in the Kentuckiana region and brief, self-report measures yielding categorical data. Conclusion: Programs servicing youth experiencing homelessness should require additional training and resources regarding the identification, screening, and assessment of youth who are at risk of or who have experienced sex trafficking in order to more quickly connect youth with much-needed, trauma-informed services.