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.

Substance use by homeless clinic attenders in Sydney.

OBJECTIVE: Describe patterns of substance use and comorbid conditions among clinic attenders in homeless shelters in Sydney. METHOD: Retrospective cohort study of 2498 people who attended a psychiatric clinic at one of three homeless hostels between February 2008 and May 2020. Multivariable logistic regression was used to identify factors associated with self-reported substance use, psychiatric diagnosis and measures of social function. RESULTS: A total of 2041 of the 2498 (81.7%) reported the harmful use of at least one substance, with alcohol (61.8%), cannabis (50.9%) and stimulant drugs (34.9%) the three most common. Those reporting the regular use of two or more substances (1466, 58.7%) were more likely to have a history of early life and adult trauma, a diagnosis of personality disorder, a criminal conviction, receive the Disability Support Pension, be chronically homeless and sleep in the open. CONCLUSIONS: The study found a high rate of polysubstance use among homeless clinic attenders in Sydney, and an increase in the prevalence of substance use compared to previous studies. Substance use is both a cause and a consequence of homelessness, and services to address substance use have to be part of any program to reduce homelessness and sleeping in the open.

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.

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.

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.

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.

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.

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.

Commonly-occurring polymorphisms in the COMT, DRD1 and DRD2 genes influence different aspects of motor sequence learning in humans.

Performing sequences of movements is a ubiquitous skill that involves dopamine transmission. However, it is unclear which components of the dopamine system contribute to which aspects of motor sequence learning. Here we used a genetic approach to investigate the relationship between different components of the dopamine system and specific aspects of sequence learning in humans. In particular, we investigated variations in genes that code for the catechol-O-methyltransferase (COMT) enzyme, the dopamine transporter (DAT) and dopamine D1 and D2 receptors (DRD1 and DRD2). COMT and the DAT regulate dopamine availability in the prefrontal cortex and the striatum, respectively, two key regions recruited during learning, whereas dopamine D1 and D2 receptors are thought to be involved in long-term potentiation and depression, respectively. We show that polymorphisms in the COMT, DRD1 and DRD2 genes differentially affect behavioral performance on a sequence learning task in 161 Caucasian participants. The DRD1 polymorphism predicted the ability to learn new sequences, the DRD2 polymorphism predicted the ability to perform a previously learnt sequence after performing interfering random movements, whereas the COMT polymorphism predicted the ability to switch flexibly between two sequences. We used computer simulations to explore potential mechanisms underlying these effects, which revealed that the DRD1 and DRD2 effects are possibly related to neuroplasticity. Our prediction-error algorithm estimated faster rates of connection strengthening in genotype groups with presumably higher D1 receptor densities, and faster rates of connection weakening in genotype groups with presumably higher D2 receptor densities. Consistent with current dopamine theories, these simulations suggest that D1-mediated neuroplasticity contributes to learning to select appropriate actions, whereas D2-mediated neuroplasticity is involved in learning to inhibit incorrect action plans. However, the learning algorithm did not account for the COMT effect, suggesting that prefrontal dopamine availability might affect sequence switching via other, non-learning, mechanisms. These findings provide insight into the function of the dopamine system, which is relevant to the development of treatments for disorders such as Parkinson's disease. Our results suggest that treatments targeting dopamine D1 receptors may improve learning of novel sequences, whereas those targeting dopamine D2 receptors may improve the ability to initiate previously learned sequences of movements.

Subjective well-being in older adults: folate and vitamin B12 independently predict positive affect.

Vitamin B12, folate and homocysteine have long been implicated in mental illness, and growing evidence suggests that they may play a role in positive mental health. Elucidation of these relationships is confounded due to the dependence of homocysteine on available levels of vitamin B12 and folate. Cross-sectional and longitudinal relationships between vitamin B12, folate, homocysteine and subjective well-being were assessed in a sample of 391 older, community-living adults without clinically diagnosed depression. Levels of vitamin B12, but not folate, influenced homocysteine levels 18 months later. Vitamin B12, folate and their interaction significantly predicted levels of positive affect (PA) 18 months later, but had no impact on the levels of negative affect or life satisfaction. Cross-sectional relationships between homocysteine and PA were completely attenuated in the longitudinal analyses, suggesting that the cross-sectional relationship is driven by the dependence of homocysteine on vitamin B12 and folate. This is the first study to offer some evidence of a causal link between levels of folate and vitamin B12 on PA in a large, non-clinical population.

Cognitive abilities in preterm and term-born adolescents.

OBJECTIVE: To investigate the influence of a range of prenatal and postnatal factors on cognitive development in preterm and term-born adolescents. STUDY DESIGN: Woodcock-Johnson III Tests of Cognitive Abilities were used to assess general intellectual ability and 6 broad cognitive abilities in 145 young adolescents aged approximately 12.5 years and born 25-41 weeks gestational age (GA). To study potential links between neurophysiologic and cognitive outcomes, corticomotor excitability was measured using transcranial magnetic stimulation and surface electromyography. The influence of various prenatal and postnatal factors on cognitive development was investigated using relative importance regression modeling. RESULTS: Adolescents with greater GA tended to have better cognitive abilities (particularly general intellectual ability, working memory, and cognitive efficiency) and higher corticomotor excitability. Corticomotor excitability explained a higher proportion of the variance in cognitive outcome than GA. But the strongest predictors of cognitive outcome were combinations of prenatal and postnatal factors, particularly degree of social disadvantage at the time of birth, birthweight percentile, and height at assessment. CONCLUSIONS: In otherwise neurologically healthy adolescents, GA accounts for little interindividual variability in cognitive abilities. The association between corticomotor excitability and cognitive performance suggests that reduced connectivity, potentially associated with brain microstructural abnormalities, may contribute to cognitive deficits in preterm children. It remains to be determined if the effects of low GA on cognitive outcomes attenuate over childhood in favor of a concomitant increase in the relative importance of heritability, or alternatively, if cognitive development is more heavily influenced by the quality of the postnatal environment.

Cognitive performance in older adults is inversely associated with fish consumption but not erythrocyte membrane n-3 fatty acids.

Higher n-3 (ω-3) polyunsaturated fatty acids (PUFAs) and fish intake may help maintain cognitive function in older age. However, evidence is inconsistent; few studies have examined the relation in cognitively healthy individuals across numerous cognitive domains, and none to our knowledge have considered lifetime fish intake. We examined associations between multiple domains of cognition and erythrocyte membrane n-3 PUFA proportions and historical and contemporary fish intake in 390 normal older adults, analyzing baseline data from the Older People, Omega-3, and Cognitive Health trial. We measured n-3 PUFA in erythrocyte membranes, and we assessed historical and contemporary fish intake by food-frequency questionnaires. We assessed cognitive performance on reasoning, working memory, short-term memory, retrieval fluency, perceptual speed, simple/choice reaction time, speed of memory-scanning, reasoning speed, inhibition, and psychomotor speed. Cognitive outcomes for each construct were factor scores from confirmatory factor analysis. Multiple linear regression models controlled for a number of potential confounding factors, including age, education, sex, apolipoprotein E-ε 4 allele, physical activity, smoking, alcohol intake, socioeconomic variables, and other health-related variables. Higher erythrocyte membrane eicosapaentonoic acid proportions predicted slower perceptual and reasoning speed in females, which was attenuated once current fish intake was controlled. No other associations were present between n-3 PUFA proportions and cognitive performance. Higher current fish consumption predicted worse performance on several cognitive speed constructs. Greater fish consumption in childhood predicted slower perceptual speed and simple/choice reaction time. We found no evidence to support the hypothesis that higher proportions of long-chain n-3 fatty acids or fish intake benefits cognitive performance in normal older adults.

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.

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.