Probing Structural Transformations and Degradation Mechanisms by Direct Observation in SIFSIX-3-Ni for Direct Air Capture.

Despite global efforts to reduce carbon dioxide (CO2) emissions, continued industrialization threatens to exacerbate climate change. This work investigates methods to capture CO2, with a focus on the SIFSIX-3-Ni metal-organic framework (MOF) as a direct air capture (DAC) sorbent. SIFSIX-3-Ni exhibits promising CO2 adsorption properties but suffers from degradation processes under accelerated aging, which are akin to column regeneration conditions. Herein, we have grown the largest SIFSIX-3-Ni single crystals to date, facilitating single crystal X-ray diffraction analyses that enabled direct observation of the H2O and CO2 dynamics through adsorption and desorption. In addition, a novel space group (I4/mcm) for the SIFSIX-3-Ni is identified, which provided insights into structural transitions within the framework and elucidated water's role in degrading CO2 uptake performance as the material ages. In situ X-ray scattering methods revealed long-range and local structural transformations associated with CO2 adsorption in the framework pores as well as a temperature-dependent desorption mechanism. Pair distribution function analysis revealed a partial decomposition to form nonporous single-layer nanosheets of edge-sharing nickel oxide octahedra upon aging. The formation of these nanosheets is irreversible and reduces the amount of active material for the CO2 sorption. These findings provide crucial insights for the development of efficient and stable DAC sorbents, effectively reducing greenhouse gases, and suggest avenues for enhancing MOF stability under practical DAC conditions.

The role of self-reliance and denial in the help-seeking process for eating disorders among university students.

OBJECTIVE: This study investigated how self-reliance and denial influence the relationship between help-seeking attitudes and behaviour. METHOD: Australian university students (N = 406) completed an online survey and females with elevated eating disorder (ED) concerns and high impairment were included in the study (N = 137). Participants completed measures of help-seeking attitudes, perceived barriers, and actual help-seeking behaviour. Via moderated logistic regression, we examined self-reliance and denial as perceived barriers to help-seeking. RESULTS: Of the total sample, over 33.7% of university students reported substantial ED concerns and impairment of whom 65.0% believed they needed help. While a majority reported that help-seeking would be useful (85.4%), only a minority of participants had sought professional help for their concerns (38.7%). Self-reliance and denial were frequently endorsed barriers and moderated the relationship between help-seeking attitudes and behaviours. CONCLUSION: ED concerns are common among university students and perceived barriers play a moderating role between attitudes and help-seeking. Future prevention and early intervention programs should address students' denial, while the importance of reaching out for professional help (rather than relying on themselves) could be highlighted with peer support.

Mechanical Exfoliation of Expanded Graphite to Graphene-Based Materials and Modification with Palladium Nanoparticles for Hydrogen Storage.

Hydrogen is a promising green fuel carrier that can replace fossil fuels; however, its storage is still a challenge. Carbon-based materials with metal catalysts have recently been the focus of research for solid-state hydrogen storage due to their efficacy and low cost. Here, we report on the exfoliation of expanded graphite (EG) through high shear mixing and probe tip sonication methods to form graphene-based nanomaterial ShEG and sEG, respectively. The exfoliation processes were optimized based on electrochemical capacitance measurements. The exfoliated EG was further functionalized with palladium nanoparticles (Pd-NP) for solid-state hydrogen storage. The prepared graphene-based nanomaterials (ShEG and sEG) and the nanocomposites (Pd-ShEG and Pd-sEG) were characterized with various traditional techniques (e.g., SEM, TEM, EDX, XPS, Raman, XRD) and the advanced high-resolution pair distribution function (HRPDF) analysis. Electrochemical hydrogen uptake and release (QH) were measured, showing that the sEG decorated with Pd-NP (Pd-sEG, 31.05 mC cm-2) and ShEG with Pd-NP (Pd-ShEG, 24.54 mC cm-2) had a notable improvement over Pd-NP (9.87 mC cm-2) and the composite of Pd-EG (14.7 mC cm-2). QH showed a strong linear relationship with an effective surface area to volume ratio, indicating nanoparticle size as a determining factor for hydrogen uptake and release. This work is a promising step toward the design of the high-performance solid-state hydrogen storage devices through mechanical exfoliation of the substrate EG to control nanoparticle size and dispersion.

Homelessness and predictors of criminal reoffending: A retrospective cohort study.

BACKGROUND: There are not many longitudinal studies examining people experiencing homelessness and interacting with the criminal justice system over time. AIMS: To describe the type of criminal offences committed, court outcomes, identify probable predictors of reoffending, and estimate the criminal justice costs in a cohort of homeless hostel clinic attendees. METHOD: A retrospective cohort study of 1646 people attending a homeless clinic who had had contact with the criminal justice system (CJS) in New South Wales (NSW), Australia, using linked clinic, criminal offence, health and mortality data from 1 July 2008 to 30 June 2021. Initial comparisons were made with the 852 clinic attendees without CJS contact in the period. Multivariable logistic regression was used to identify predictors of recidivism. RESULTS: There were 16,840 offending episodes, giving an offence rate of 87.8 per 100 person-years (95%CI: 86.5-89.1). The most common index offences were acts intended to cause injury (22%), illicit drug (17%) and theft-related (12%) offences. Most people (83%) were found guilty of the index offence and received a fine (37%) or community-based sentence (29%). Total court finalisation costs were AUD $11.3 million. Three-quarters of those convicted reoffended within 24 months. Offenders were more likely to be younger, have a diagnosis of personality disorder (AOR: 1.31; 95% CI: 1.04-1.67), a substance use disorder (AOR: 1.60; 95% CI 1.14-2.23) and/or to have a previous charge dismissed on mental health grounds (AOR: 1.79; 95% CI: 1.31-2.46). Within the offending cohort, reoffenders had almost twice the odds of having theft-related offences as their principal index offence (AOR: 1.85; 95% CI: 1.29-2.66). CONCLUSIONS: This longitudinal study finding of not only a high rate of criminal justice contact, but also a high rate of recidivism among people who have been homeless, lends support to a need for strategies both to address the root causes of homelessness and to provide a comprehensive systems-based response to reduce recidivism, that includes secure housing as well as mental health and substance use treatment programmes for homeless offenders.

Psychiatric rehabilitation in secure forensic settings in NSW: Measuring outcomes.

OBJECTIVE: To quantify outcomes for patients of forensic psychiatric rehabilitation in NSW. METHODS: Data on 245 conditionally released forensic patients was extracted from the Mental Health Review Tribunal (MHRT) files and matched to several state-wide datasets. Descriptive statistics were generated to establish the cohort characteristics, rates of reoffending and social and clinical outcomes. RESULTS: At conditional release, social circumstances for the majority of patients were improved. Clinically, the cohort was more stable, though many did not remain stable over time. Only one-fifth of the sample received a further criminal charge. CONCLUSION: Preliminary evidence suggests that forensic rehabilitation services in NSW are effective.

Rates and causes of mortality among the homeless in Sydney.

OBJECTIVE: To report on the rate and causes of mortality, and associations with premature mortality among the homeless in inner city Sydney. METHOD: Retrospective cohort study of 2,498 people who attended a psychiatric clinic conducted at the three main homeless hostels between 17 February 2008 and 19 May 2020. Cox's proportional hazards regression was used to identify factors associated with mortality. RESULTS: A total of 324 of the 2498 (13.0%) clinic attenders were found to have died in the follow-up period, with a mean age at death of 50.7 years. Unnatural causes of death (119/324, 36.7%) included drug overdose (24.1%), suicide (6.8%) and other injuries (5.9%), at a younger age (44.4 years) than those who died from natural causes (54.4 years). There were 142 (43.8%) deaths from natural causes and 63 (19.4%) in which the cause of death was not determined. CONCLUSIONS: The study confirms the high mortality of homeless clinic attenders in Sydney found in a study from 30 years earlier. The lower mortality among regular attenders supports the provision of accessible services to address the physical health needs of homeless people, as well as ready access to mental health and substance use services.

An inclined detector geometry for improved X-ray total scattering measurements.

X-ray total scattering measurements are implemented using a digital flat-panel area detector in an inclined geometry and compared with the traditional geometry. The traditional geometry is defined here by the incident X-ray beam impinging on and normal to the center-most pixel of a detector. The inclined geometry is defined here by a detector at a pitch angle α, set to 15° in this case, bisected by the vertical scattering plane. The detector is positioned such that the incident X-ray beam strikes the pixels along the bottom edge and 90° scattered X-rays impinge on the pixels along the top edge. The geometric attributes of the inclined geometry translate into multiple benefits, such as an extension of the measurable scattering range to 90°, a 47% increase in the accessible magnitudes of the reciprocal-space vector Q and a leveling of the dynamic range in the measured total scattering pattern. As a result, a sixfold improvement in signal-to-noise ratios is observed at higher scattering angles, enabling up to a 36-fold reduction in acquisition time. Additionally, the extent of applied modification functions is reduced, decreasing the magnitude of termination ripples and improving the real-space resolution of the pair distribution function G(r). Taken all together, these factors indicate that the inclined geometry produces higher quality data than the traditional geometry, usable for simultaneous Rietveld refinement and total scattering studies.

Multimodal image and spectral feature learning for efficient analysis of water-suspended particles.

We have developed a method to combine morphological and chemical information for the accurate identification of different particle types using optical measurement techniques that require no sample preparation. A combined holographic imaging and Raman spectroscopy setup is used to gather data from six different types of marine particles suspended in a large volume of seawater. Unsupervised feature learning is performed on the images and the spectral data using convolutional and single-layer autoencoders. The learned features are combined, where we demonstrate that non-linear dimensional reduction of the combined multimodal features can achieve a high clustering macro F1 score of 0.88, compared to a maximum of 0.61 when only image or spectral features are used. The method can be applied to long-term monitoring of particles in the ocean without the need for sample collection. In addition, it can be applied to data from different types of sensor measurements without significant modifications.

The Empowering Function of the Belief in a Just World for the Self: Trait-Level and Experimental Tests of Its Association With Positive and Negative Affect.

Belief in a just world for the self (BJW-self) is a resource that promotes adaptive functioning. We theorize that BJW-self has such an effect because it is empowering. This article reports on four studies (N = 967) testing whether BJW-self encourages more positive and less negative affect indirectly through empowerment. There was support for this hypothesis at a trait level across all studies, and specifically in Study 1. Experimental evidence, however, was more complex. Study 2 demonstrated the causal effect of the mediator, empowerment, on affect. Study 3 demonstrated that affirming BJW-self enhanced empowerment with an associated increase in positive affect and reduced negative affect. Study 4 showed that enhancing empowerment did not significantly influence the effect of affirmed BJW-self on affect, but blocking empowerment did, although this finding is qualified by no significant effect on empowerment. We discuss the theoretical implications of these findings, and the challenges of experimentally manipulating BJW-self.

Unsupervised feature learning and clustering of particles imaged in raw holograms using an autoencoder.

Digital holography is a useful tool to image microscopic particles. Reconstructed holograms give high-resolution shape information that can be used to identify the types of particles. However, the process of reconstructing holograms is computationally intensive and cannot easily keep up with the rate of data acquisition on low-power sensor platforms. In this work, we explore the possibility of performing object clustering on holograms that have not been reconstructed, i.e., images of raw interference patterns, using the latent representations of a deep-learning autoencoder and a self-organizing mapping network in a fully unsupervised manner. We demonstrate this concept on synthetically generated holograms of different shapes, where clustering of raw holograms achieves an accuracy of 94.4%. This is comparable to the 97.4% accuracy achieved using the reconstructed holograms of the same targets. Directly clustering raw holograms takes less than 0.1 s per image using a low-power CPU board. This represents a three-order of magnitude reduction in processing time compared to clustering of reconstructed holograms and makes it possible to interpret targets in real time on low-power sensor platforms. Experiments on real holograms demonstrate significant gains in clustering accuracy through the use of synthetic holograms to train models. Clustering accuracy increased from 47.1% when the models were trained only on the real raw holograms, to 64.1% when the models were entirely trained on the synthetic raw holograms, and further increased to 75.9% when models were trained on the both synthetic and real datasets using transfer learning. These results are broadly comparable to those achieved when reconstructed holograms are used, where the highest accuracy of 70% achieved when clustering raw holograms outperforms the highest accuracy achieved when clustering reconstructed holograms by a significant margin for our datasets.

The Children's Forgiveness Card Set: Development of a Brief Pictorial Card-Sorting Measure of Children's Emotional Forgiveness.

Friendships have important influences on children's well-being and future adjustment, and interpersonal forgiveness has been suggested as a crucial means for children to maintain friendships. However, existing measures of preadolescent children's forgiveness are restricted by developmental limitations to reporting emotional responses via questionnaire and inconsistent interpretations of the term "forgive." This paper describes development and testing of concurrent and discriminant validity of a pictorial measure of children's emotional forgiveness, the Children's Forgiveness Card Set (CFCS). In Study 1, 148 Australian children aged 8-13 years (M = 10.54, SD = 1.35) responded to a hypothetical transgression in which apology was manipulated and completed the CFCS and extant measures of forgiveness and socially desirable responding. Following an exploratory factor analysis to clarify the structure of the CFCS, the CFCS correlated moderately with other forgiveness measures and did not correlate with socially desirable responding. Apology predicted CFCS responding among older children. In Study 2 an exploratory factor analysis broadly replicated the structure of the CFCS among a sample of N = 198 North American children aged 5-14 years (M = 9.39 years, SD = 1.67). We also fitted an exploratory bi-factor model to the Study 2 data which clarified which cards best measured general forgiveness, or positive or hostile aspects of responding to transgressions. Apology once again predicted the CFCS, this time regardless of age. The CFCS appears a potentially valid measure of children's emotional forgiveness. Potential applications and differences between explicit and latent forgiveness in children are discussed.

Identification of microplastics in a large water volume by integrated holography and Raman spectroscopy.

A noncontact method to identify sparsely distributed plastic pellets is proposed by integrating holography and Raman spectroscopy in this study. Polystyrene and poly(methyl methacrylate) resin pellets with a size of 3 mm located in a 20 cm water channel were illuminated using a collimated continuous wave laser beam with a diameter of 4 mm and wavelength of 785 nm. The same laser beam was used to take a holographic image and Raman spectrum of a pellet to identify the shape, size, and composition of material. Using the compact system, the morphological and chemical analysis of pellets in a large volume of water was performed. The reported method demonstrates the potential for noncontact continuous in situ monitoring of microplastics in water without collection and separation.

Mackintosh, pearce-hall and time: An EEG study on Inhibition of return.

We investigated whether the temporal dynamics of attention could be used to reconcile exploitative and explorative attentional learning theories. Participants trained on a categorisation task where some stimuli were predictive (P) of the correct response while others were non-predictive (NP). These stimuli were then used in a dot probe task in which we varied the stimulus onset asynchrony (SOA) between the cues and the target. Participants responded faster to the target when it appeared over a P cue at each SOA. The reaction time advantage towards the P cues increased proportionally with SOA, suggesting that participants were strategically processing the cues. Target-elicited N2pc amplitudes at short SOAs suggested that P cues were preferentially processed, consistent with exploitation. However, the amplitudes at a longer SOA suggested that after the P cues were processed, they were inhibited. This inhibition could bias attention towards other currently ambiguous stimuli, consistent with exploration.

Polymorphisms in dopaminergic genes predict proactive processes of response inhibition.

The ability to inhibit a prepared emotional or motor action is difficult but critical to everyday functioning. It is well-established that response inhibition relies on the dopaminergic system in the basal ganglia. However, response inhibition is often measured imprecisely due to a process which slows our responses and increases subsequent inhibition success known as proactive inhibition. As the role of the dopamine system in proactive inhibition is unclear, we investigated the contribution of dopaminergic genes to proactive inhibition. We operationalised proactive inhibition as slower responses after failures to inhibit a response in a Go/No-Go paradigm and investigated its relationship to rs686/A at DRD1 (associated with increased gene expression) and rs1800497/T at DRD2 (associated with reduced D2 receptor availability). Even though our sample (N = 264) was relatively young (18-40 years), we found that proactive inhibition improves the ability to withhold erroneous responses in older participants (p = 0.002) and those with lower fluid intelligence scores (p < 0.001), indicating that proactive inhibition is likely a naturally occurring compensatory mechanism. Critically, we found that a polygenic risk score consisting of the number of rs686 A and rs1800497 T alleles predicts higher engagement of proactive inhibition (p = 0.040), even after controlling for age (p = 0.011). Furthermore, age seemed to magnify these genetic effects (p < 0.001). This suggests that the extent to which proactive inhibition is engaged depends on increased dopamine D1 and decreased D2 neurotransmission. These results provide important considerations for future work investigating disorders of the dopaminergic system.

Individual differences in anxiety and fear learning: The role of working memory capacity.

Anxiety disorders are characterised by the perception of fear and threat in the presence of stimuli that are neutral or ambiguous. Attempts in previous research to explain the relationship between anxiety and fear learning have been inconsistent, possibly due to the influence of an unmeasured mechanism that mediates the relationship between them. Working memory capacity has been suggested as one such mechanism. The current study investigated the influence of anxiety-based individual differences upon associative fear learning, while accounting for individual differences in working memory. We hypothesised that individuals high in both anxiety and working memory would show unimpaired fear learning whereas individuals high in anxiety and low in working memory would exhibit dysfunctional fear learning. Sixty participants completed a battery of anxiety and working memory tests, as well as a fear conditioning experiment that tested for blocking, conditioned inhibition and fear discrimination. We found that anxious individuals were more likely to show impaired fear discrimination only if they also had a low working memory capacity. Furthermore, anxiety was particularly associated with poorer learning about safety cues. Such relationships were not observed for blocking and conditioned inhibition. These results suggest that the relationship between anxiety and fear learning is complex and warrants further investigation of the potential mediating role of higher-order cognitive faculties.

Polymorphisms that affect GABA neurotransmission predict processing of aversive prediction errors in humans.

Learning is one of our most adaptive abilities, allowing us to adjust our expectations about future events. Aberrant learning processes may underlie disorders such as anxiety, motivating the search for the neural mechanisms that underpin learning. Animal studies have shown that the neurotransmitter GABA is required for the computation of prediction errors, the mismatches between anticipated and experienced outcomes, which drive new learning. Given that evidence from human studies is lacking, we sought to determine whether these findings extend to humans. Here, in two samples of Caucasian individuals, we investigated whether genetically determined individual differences in GABA neurotransmission predict the P3 event-related potential, an EEG component known to reflect prediction error processing. Consistent with the results of animal studies, we show that a weighted genetic risk score computed from the number of GABRB2 rs1816072 A alleles (associated with increased expression of the GABAA receptor ß2 subunit gene) and the number of ErbB4 rs7598440 T alleles (associated with increased GABA concentration) predicts optimal prediction error processing during aversive classical conditioning with both visual (Experiment 1, N = 90; p = .010) and auditory (Experiment 2; N = 92; p = .031) unconditioned stimuli. Our finding that optimal processing of aversive prediction errors is reduced in individuals genetically predisposed towards decreased GABA neurotransmission suggests a potential mechanism linking GABA and anxiety. Specifically, reduced GABA signalling via GABAA receptors could result in aberrant learning from aversive experiences and vulnerability to anxiety disorders.

Characteristics of people attending psychiatric clinics in inner Sydney homeless hostels.

OBJECTIVE: To describe the characteristics of people attending mental health clinics at shelters for the homeless in inner city Sydney. DESIGN: Retrospective review of medical records of homeless hostel clinic attenders. SETTING: Mental health clinics located in three inner city homeless hostels. PARTICIPANTS: Consecutive series of clinic attenders, 21 July 2008 - 31 December 2016. MAIN OUTCOME MEASURES: Demographic characteristics; social, medical and mental health histories of homeless people. RESULTS: 2388 individual patients were seen at the clinics during the 8.5-year study period. Their mean age was 42 years (standard deviation, 13 years), 93% were men, and 56% were receiving disability support pensions. 59% of attenders had been homeless for more than a year, and 34% of all attenders reported sleeping in the open. The most common diagnoses were substance use disorder (66%), psychotic illness (51%), acquired brain injury (14%), and intellectual disability (5%). Most patients had more than one diagnosis. Early life and recent trauma was reported by 42% of patients. Pathways to homelessness included release from prison (28% of the homeless), discharge from a psychiatric hospital (21%), loss of public housing tenancy (21%), and inability to pay rent because of problem gambling. CONCLUSIONS: The high rates of substance use and mental disorder among homeless people in inner Sydney confirms the need for increased access to treatment for these conditions in this setting. Homelessness among those with mental illness might be reduced by developing alternative housing models, and supporting people with multiple problems to retain tenancy.

Age-related differences in sequence learning: Findings from two visuo-motor sequence learning tasks.

The Serial Reaction Time Task (SRTT) is thought to assess implicit learning, which seems to be preserved with age. However, the reaction time (RT) measures employed on implicit-like tasks might be too unreliable to detect individual differences. We investigated whether RT-based measures mask age effects by comparing the performance of 43 younger and 35 older adults on SRTT and an explicit-like Predictive Sequence Learning Task (PSLT). RT-based measures (difference scores and a ratio) were collected for both tasks, and accuracy was additionally measured for PSLT. We also measured fluid abilities. The RT-difference scores indicated preserved SRTT and PSLT performance with age and did not correlate with fluid abilities, while ratio RT and the accuracy-based measures indicated age-related decline and correlated with fluid abilities. Therefore, RT-difference scores might mask individual differences, which compromises the interpretation of previous studies using SRTT.

Fluid Abilities and Rule Learning: Patterning and Biconditional Discriminations.

Previous experience with discrimination problems that can only be solved by learning about stimulus configurations enhances performance on new configural discriminations. Some of these effects can be explained by a shift toward increased configural processing (learning about combinations of cues rather than about individual elements), or by a tendency to generalize a learned rule to a new training set. We investigated whether fluid abilities influence the extent that previous experience with configural discriminations improves performance on subsequent discriminations. In Experiments 1 and 2 we used patterning discriminations that could be solved by applying a simple rule, whereas in Experiment 3 we used biconditional discriminations that could not be solved using a rule. Fluid abilities predicted the improvement on the second training set in all experiments, including Experiment 3 in which rule-based generalization could not explain the improvement on the second discrimination. This supports the idea that fluid abilities contribute to performance by inducing a shift toward configural processing rather than rule-based generalization. However, fluid abilities also predicted performance on a rule-based transfer test in Experiment 2. Taken together, these results suggest that fluid abilities contribute to both a flexible shift toward configural processing and to rule-based generalization.