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Whereas single crystals of organic compounds that respond to heat or light have been reported and studied in detail, studies on crystalline organic compounds that elicit an extreme mechanical response upon cooling to very low temperaturesare relatively rare in the chemical literature. A tetrafluoro(aryl)sulfanylated bicyclopentane synthesized in our laboratory was discovered to exhibit such behavior; i.e., the crystals jumped and forcefully disintegrated upon cooling below ∼193 K. Accordingly, the origin of this low-temperature thermosalient effect was investigated through NMR, SC-XRD, PXRD, microscopy, DSC, Raman, and Brillouin experiments. To our surprise, NMR, SC-XRD, PXRD, and DSC experiments suggest the phenomenon can neither be attributed solely to a chemical transformation nor a phase transition of the entire material. Rather, XRD, Raman, and Brillouin experiments provide evidence that built-up strain released from the crystal upon self-destruction may be associated with crystal microstructure or a phase transition that occurs in another material (i.e., an impurity) in the crystal. This study demonstrates that molecular structural changes in organic material microstructure or impurity phases (which may not necessarily be visible by X-ray diffraction) can have a significant impact on the behavior of the bulk crystalline material. Thus, the role of microstructure may be considered more heavily in future mechanistic studies on mechanically responsive crystals.

Spontaneous phase separation of materials is a powerful strategy to generate highly defined 2D nanomorphologies with novel properties and functions. Exemplary are such morphologies in block copolymers or amphiphilic systems, whose formation can be well predicted based on parameters such as volume fraction and shape factor. In contrast, the formation of 2D nanomorphologies is currently unpredictable in materials perfectly defined at the molecular level, in which crystallinity plays a significant role. Here, we introduce a crystal lattice analysis to predict a priori the formation of 2D nanomorphologies from the crystalline units in phase-separated soft materials. We show that the formation of lamellar morphologies, their domain spacings, and thermal transition temperatures of such materials can be predicted using a straightforward crystal lattice analysis workflow. We envision this approach to facilitate the design and discovery of new materials with 2D nanomorphologies that are essential for next-generation electronic applications.

A ‘Black Out Rage Gallon’ (borg) is a customised, individual alcoholic beverage popularised on TikTok, whereby half the water in a gallon jug is replaced with alcohol (usually spirits), flavourings, electrolytes and caffeine. We investigated the characteristics and portrayal of the emerging alcohol trend associated with the hashtag descriptor #borg on TikTok. We identified highly viewed TikTok videos with the #borg hashtag (n= 103) and conducted a content analysis, capturing viewer engagement (‘likes’, shares, comments), techniques used, characteristics of featured individuals, and the portrayal of alcohol and risky drinking behaviours. Alcohol was visible in three quarters of the videos analysed (n= 78, average amount of alcohol present 865 mL per borg) and consumed in one third of the videos (n= 34). One quarter of videos (n= 25) promoted alleged benefits of borg consumption compared to other alcohol products or approaches to drinking, yet only nine videos included a warning about potential harms. The borg trend on TikTok may encourage risky drinking, by portraying it in a style that younger viewers are likely to see as fun and entertaining. We were able to gain a better understanding of how this potentially health harming activity is represented on a social media platform that is popular with young people. The speedy dissemination of this trend highlights the need to monitor, investigate and counter emerging trends. Concurrently, there is an urgent need for content restrictions to limit the visibility and promotion of risky alcohol consumption on TikTok.

Rivers are a key component of the global carbon cycle. They receive vast quantities of terrestrial carbon, of which a large fraction is ultimately exported to the coastal ocean. Our review of previously published assessments reveals that substantial uncertainties remain with regard to the spatial distribution and speciation of the carbon export. Accurate quantification of the relative contributions of dissolved, particulate, organic and inorganic carbon to the total amounts is, however, of crucial importance for the coupling between the terrestrial and marine carbon cycles. Breaking down existing spatially explicit assessments over large river basins, we find a disagreement in flux estimates that exceeds two orders of magnitude for more than half of the basins. Using machine-learning techniques in combination with a multi-model ensemble and an updated database of observations, we overcome the inconsistencies in existing assessments and narrow down uncertainties in riverine carbon exports. Our revised assessment yields a global riverine export of 1.02 ± 0.22 (2σ) PgC yr−1. This carbon flux is partitioned into 0.52 ± 0.17, 0.30 ± 0.14, 0.18 ± 0.04 and 0.03 ± 0.02 PgC yr−1of dissolved inorganic, dissolved organic, particulate organic and particulate inorganic carbon, respectively. We estimate the carbon contribution through groundwater export to be minor (0.016 PgC yr−1). Our assessment suggests an underestimation of the land-to-ocean carbon flux by 0.24 PgC yr−1by the Intergovernmental Panel on Climate Change (IPCC) and calls for a revision of the oceanic carbon budget.

Phenol-based macrocycles play a fundamental role in supramolecular chemistry, but their size has been rather limited. Here we report a novel class of very large, bowl-shaped macrocycles with a diameter of 21.8 Å. These quinoacridane[4]arenes are 150% larger than the current record holders, the acridane[4]arenes, and three times the size of resorcin[4]arene. We expect the quinoacridane[4]arenes to be a useful platform for the construction of molecular containers.

Transcranial magnetic stimulation (TMS) is used to treat several neuropsychiatric disorders including depression, where it is effective in approximately one half of patients for whom pharmacological approaches have failed. Treatment response is related to stimulation parameters such as the stimulation frequency, pattern, intensity, location, total number of pulses and sessions applied, and target brain network engagement. One critical but underexplored component of the stimulation procedure is the orientation or yaw angle of the commonly used figure-of-eight TMS coil, which is known to impact neuronal response to TMS. However, coil orientation has remained largely unchanged since TMS was first used to treat depression and continues to be based on motor cortex anatomy, which may not be optimal for the dorsolateral prefrontal cortex treatment site. In this targeted narrative review, we evaluate experimental, clinical, and computational evidence indicating that optimizing coil orientation may improve TMS treatment outcomes. The properties of the electric field induced by TMS, the changes to this field caused by the differing conductivities of head tissues, and the interaction between coil orientation and the underlying cortical anatomy are summarized. We describe evidence that the magnitude and site of cortical activation, surrogate markers of TMS dosing and brain network targeting considered central in clinical response to TMS, are influenced by coil orientation. We suggest that coil orientation should be considered when applying therapeutic TMS and propose several approaches to optimizing this potentially important treatment parameter.

Using apples as a raw material and its by-products, such as pomace, in the development of innovative products and drinks, contributes to the production chain of this fruit. The objective of this research was to evaluate physicochemical characteristics, phenolic and profile sensory in aged apple liqueur, prepared with different formulations. Liqueurs were produced using depectinized apple juice, integral apple juice, pectinolytic enzyme and dehydrated apple pomace, all with a final sugar concentration of 100 g/L and an alcohol content of 20% v/v. All received chips (1 cm³) of untoasted oak wood (5 g/L), for maturation for 120 days. The use of an ultrasonic probe was tested in the pre-treatment of wood chips as well as dehydrated apple pomace. Analyzes of acidity, pH, density, total sugar, individual compound profile, total phenols, antioxidant activity and color parameters were carried out. Sensory analysis was applied using the JAR methodology along with acceptability. The results showed that liqueurs made with depectinized juice presented the highest values of total phenols (191.03 mg EAC/L) and antioxidant activity (1001.32 µmol TE/L by DPPH, 1376.70 by FRAP and 1857.41 by ABTS). The liqueurs that received pomace, at the end of the maturation period, showed high luminosity (L* = 96.1) and a light-yellow tone (b* = 35.31). The action of the ultrasonic probe under the wood chips was evidenced with a 3% increase in total phenols and a 5% increase in antioxidant activity. The liqueur that used integral juice and pectinolytic enzyme in the formulation had greater color intensity (C* = 42.6) and a more prominent shade of yellow (b*= 42.66). Finally, formulating the liqueurs with depectinized juice contributes to greater color intensity and maturing the liqueurs with wood chips pre-treated with an ultrasonic device contributed to the incorporation of compounds, improving the concentration of total phenols, and increasing antioxidant activity.

Transcranial magnetic stimulation (TMS) is increasingly used as a noninvasive technique for neuromodulation in research and clinical applications, yet its mechanisms are not well understood. Here, we present the neurophysiological effects of TMS using intracranial electrocorticography (iEEG) in neurosurgical patients. We first evaluated safety in a gel-based phantom. We then performed TMS-iEEG in 22 neurosurgical participants with no adverse events. We next evaluated intracranial responses to single pulses of TMS to the dorsolateral prefrontal cortex (dlPFC) (N= 10, 1414 electrodes). We demonstrate that TMS is capable of inducing evoked potentials both locally within the dlPFC and in downstream regions functionally connected to the dlPFC, including the anterior cingulate and insular cortex. These downstream effects were not observed when stimulating other distant brain regions. Intracranial dlPFC electrical stimulation had similar timing and downstream effects as TMS. These findings support the safety and promise of TMS-iEEG in humans to examine local and network-level effects of TMS with higher spatiotemporal resolution than currently available methods.

Genome-wide association studies (GWASs) of major depressive disorder (MDD) have recently achieved extremely large sample sizes and yielded substantial numbers of genome-wide significant loci. Because of the approach to ascertainment and assessment in many of these studies, some of these loci appear to be associated with dysphoria rather than with MDD, potentially decreasing the clinical relevance of the findings. An alternative approach to MDD GWAS is to focus on the most severe forms of MDD, with the hope that this will enrich for loci of larger effect, rendering their identification plausible, and providing potentially more clinically actionable findings. Here we review the genetics of severe depression by using clinical markers of severity including: age of onset, recurrence, degree of impairment, and treatment with ECT. There is evidence for increased family-based and Single Nucleotide Polymorphism (SNP)-based estimates of heritability in recurrent and early-onset illness as well as severe functional impariment. GWAS have been performed looking at severe forms of MDD and a few genome-wide loci have been identified. Several whole exome sequencing studies have also been performed, identifying associated rare variants. Although these findings have not yet been rigorously replicated, the elevated heritability seen in severe MDD phenotypes suggests the value of pursuing additional genome-wide interrogation of samples from this population. The challenge now is generating a cohort of adequate size with consistent phenotyping that will allow for careful and robust classifications and distinctions to be made. We are currently pursuing such a strategy in our 50-site worldwide Gen-ECT-ics consortium.

Responding by individuals in groups has been a prominent interest of the field of psychology. Experimental analyses of human behavior have provided some unique findings of the role that the environment, including both social and nonsocial stimuli, may have on individual responding. Cooperative and competitive contingencies, previously evaluated in animal and human operant research, provide unique insight into applied interventions, in particular group contingencies. The current manuscript attempts to bridge these two literatures to foster the development of more effective technologies and lines of experimental or translational research that may better inform interventions in the applied realm.

Topic models are a class of unsupervised learning algorithms for detecting the semantic structure within a text corpus. Together with a subsequent dimensionality reduction algorithm, topic models can be used for deriving spatializations for text corpora as two-dimensional scatter plots, reflecting semantic similarity between the documents and supporting corpus analysis. Although the choice of the topic model, the dimensionality reduction, and their underlying hyperparameters significantly impact the resulting layout, it is unknown which particular combinations result in high-quality layouts with respect to accuracy and perception metrics. To investigate the effectiveness of topic models and dimensionality reduction methods for the spatialization of corpora as two-dimensional scatter plots (or basis for landscape-type visualizations), we present a large-scale, benchmark-based computational evaluation. Our evaluation consists of (1) a set of corpora, (2) a set of layout algorithms that are combinations of topic models and dimensionality reductions, and (3) quality metrics for quantifying the resulting layout. The corpora are given as document-term matrices, and each document is assigned to a thematic class. The chosen metrics quantify the preservation of local and global properties and the perceptual effectiveness of the two-dimensional scatter plots. By evaluating the benchmark on a computing cluster, we derived a multivariate dataset with over 45 000 individual layouts and corresponding quality metrics. Based on the results, we propose guidelines for the effective design of text spatializations that are based on topic models and dimensionality reductions. As a main result, we show that interpretable topic models are beneficial for capturing the structure of text corpora. We furthermore recommend the use of t-SNE as a subsequent dimensionality reduction.

Adolescents are heavily exposed to unhealthy outdoor food advertisements near schools, however, the marketing power of these advertisements among adolescents has not yet been explored. This study aimed to investigate the teen‐directed marketing features present and quantify the overall marketing power of outdoor food advertisements located near schools to explore any differences by content (ie, alcohol, discretionary, core and miscellaneous foods) school type (ie, primary, secondary, K‐12) and area‐level socio‐economic status (SES; ie, low vs high). This cross‐sectional study audited every outdoor food advertisement (n = 1518) within 500m of 64 randomly selected schools in Perth, Western Australia, using a teen‐informed coding tool to score the marketing power of each advertisement. Outdoor alcohol advertisements around schools had the highest average marketing power score and number of advertising features present. Outdoor advertisements for alcohol and discretionary foods scored significantly higher in marketing power than core food advertisements (P < .001). Outdoor alcohol advertisements around secondary schools scored significantly higher in marketing power than around primary and K‐12 schools (P< .001); and outdoor advertisements for discretionary foods in low SES areas scored significantly higher in marketing power than those in high SES areas (P< .001). This study found outdoor advertisements for unhealthy products, such as alcohol and discretionary foods, were more powerful than advertisements for core foods around schools. These findings strengthen the need for policies which restrict outdoor advertisements for non‐core foods near schools, to reduce adolescents' exposure to powerful alcohol and discretionary food advertisements.

The purpose of this study is to define departmental action limits for energy percentage variation measured by means of step-wedge helical Tomotherapy quality assurance module. Individual charts using the Statistical Process Control techniques have been used to identify retrospectively out-of-control situations ascribable to documented actions performed on the Tomotherapy system. Using the in-control data of our analysis process capability indices (cp, cpk, cpmand cpmk) are calculated in order to document the real working condition of the Tomotherapy system. Our findings indicate use of an action limit of 1.0% for energy percentage variation difference between the measured and reference output is a good working condition of a Tomotherapy system. cpand cpkindices are suggested as good indices that correctly report the system capability. A method for calculating and reporting Tomotherapy action limits for the integrated self-checking TQA energy check was shown in this study. SPC technique has proven to be efficient in defining departmental action limits from retrospective data for TQA energy measurements, hence optimally enabling corrective improvements in the process of quality assurance.

Transit monitoring is a preventive approach used to identify possible cases of human trafficking before exploitation while an individual is in transit or before crossing a border. Transit monitoring is often conducted by nongovernmental organizations (NGOs) that train staff to identify and intercept suspicious activity. Love Justice International (LJI) is a well-established NGO that has been conducting transit monitoring for years along the Nepal-India border at multiple monitoring stations. In partnership with LJI, we developed a system that uses data envelopment analysis (DEA) to help LJI decision makers evaluate the performance of these stations at intercepting potential human trafficking victims given the amount of resources (staff, etc.) available and make specific operational improvement recommendations. Our model consists of 91 decision-making units from seven stations over 13 quarters and considers three inputs, four outputs, and three homogeneity criteria. Using this model, we identified efficient stations, compared rankings of station performance, and recommended strategies to improve efficiency. To the best of our knowledge, this is the first application of DEA in the anti-human trafficking domain.History:This paper was refereed.Funding:This material is based upon work supported by the National Science Foundation [Grant CMMI-1841893].

Life as we know it is built on complex and perfectly interlocking processes that have evolved over millions of years through evolutionary optimization processes. The emergence of life from nonliving matter and the evolution of such highly efficient systems therefore constitute an enormous synthetic and systems chemistry challenge. Advances in supramolecular and systems chemistry are opening new perspectives that provide insights into living and self-sustaining reaction networks as precursors for life. However, the ab initio synthesis of such a system requires the possibility of autonomous optimization of catalytic properties and, consequently, of an evolutionary system at the molecular level. In this Account, we present our discovery of the formation of substituted imidazolidine-4-thiones (photoredox) organocatalysts from simple prebiotic building blocks such as aldehydes and ketones under Strecker reaction conditions with ammonia and cyanides in the presence of hydrogen sulfide. The necessary aldehydes are formed from CO2and hydrogen under prebiotically plausible meteoritic or volcanic iron-particle catalysis in the atmosphere of the early Earth. Remarkably, the investigated imidazolidine-4-thiones undergo spontaneous resolution by conglomerate crystallization, opening a pathway for symmetry breaking, chiral amplification, and enantioselective organocatalysis. These imidazolidine-4-thiones enable α-alkylations of aldehydes and ketones by photoredox organocatalysis. Therefore, these photoredox organocatalysts are able to modify their aldehyde building blocks, which leads in an evolutionary process to mutated second-generation and third-generation catalysts. In our experimental studies, we found that this mutation can occur not only by new formation of the imidazolidine core structure of the catalyst from modified aldehyde building blocks or by continuous supply from a pool of available building blocks but also by a dynamic exchange of the carbonyl moiety in ring position 2 of the imidazolidine moiety. Remarkably, it can be shown that by incorporating aldehyde building blocks from their environment, the imidazolidine-4-thiones are able to change and adapt to altering environmental conditions without undergoing the entire formation process. The selection of the mutated catalysts is then based on the different catalytic activities in the modification of the aldehyde building blocks and on the catalysis of subsequent processes that can lead to the formation of molecular reaction networks as progenitors for cellular processes. We were able to show that these imidazolidine-4-thiones not only enable α-alkylations but also facilitate other important transformations, such as the selective phosphorylation of nucleosides to nucleotides as a key step leading to the oligomerization to RNA and DNA. It can therefore be expected that evolutionary processes have already taken place on a small molecular level and have thus developed chemical tools that change over time, representing a hidden layer on the path to enzymatically catalyzed biochemical processes.

AbstractThe transformation of urban infrastructures, such as water, energy and transport, is central for the sustainable development of cities. Those responsible for the provision of public services are increasingly under pressure to transform infrastructures to make them more sustainable. Our paper explores governance-related challenges and solutions to transforming urban infrastructures in the context of the city state of Berlin. In the form of case studies, we investigate three transdisciplinary research projects that attempt to support transformation processes in the water, energy and transport sectors respectively. The analysis draws on reports and publications, discussion with central actors from the projects as well as the city administration between 2017 and 2022. Despite differences between the projects as well as the infrastructure systems addressed, we identify some common barriers for the transformation of urban infrastructures in the city state of Berlin. Results show that local neighbourhoods are important socio-spatial units for catalysing transformation processes. They allow for experiments with more sustainable infrastructure configurations and novel governance approaches. However, these niche experiments do not scale to the mainstream, yet. Across the three infrastructure systems, we discuss potential solutions and conclude with reflections on the implications for the sustainable transformation of urban infrastructures in Berlin and beyond.English title: Transformation of urban infrastructures. Barriers and solutions from three transdisciplinary research projects on networked infrastructures in Berlin

Energy drinks (EDs) are not recommended for children due to their high caffeine content and adverse health risks. Their popularity among children may be due to children's exposure to ED marketing. This study aimed to identify where children have seen ED marketing and whether they believe ED marketing targets them. Participant data were drawn from ‘AMPED UP: An Energy Drink Study’, where 3688 students in grades 7–12 (age 12–17 years) from 25 randomly selected secondary schools in Western Australia were asked if they had ever seen ED advertising on television, posters/signs in shops, online/internet, movies, cars/vehicles, social media, magazines/newspapers, music videos, video games, merchandise and free samples. Participants were also shown three ED advertisements and asked, ‘Which age group/s do you think this ad targets?’ (12 years or less, 13–17 years, 18–23 years, 24 years or older) and could select multiple age groups for each advertisement. On average, participants saw ED advertising on 6.5 (SD = 2.5) of 11 possible marketing channels, including television (seen by 91% of participants), posters/signs in shops (88%), online/internet (82%) and movies (71%). Participants also perceived ED advertisements targeted children (< 18 years). ED marketing has a high reach among Western Australian children. The voluntary ED advertising pledge to not market EDs to children in Australia does not prevent children from seeing or being targeted by ED marketing. Stronger regulatory control of ED marketing is needed to better protect children from the appeal and adverse health risks of ED use.

•L:R ratios rise after conditioning, independent of regimen or diagnosis, and return to baseline by day +30 in most patients receiving allogeneic HSCT.•Intestinal permeability correlates directly with LBP levels and inversely with dysbiosis.

Die physikalischen Eigenschaften pneumatischer Antriebe ermöglichen den Bau von sicheren, leichten und intuitiv bedienbaren Robotern, deren Regelung jedoch herausfordernd ist. Gründe dafür sind die Dynamik der Pneumatik und nichtlineare Reibung mit Unsicherheiten, die ohne abtriebsseitige Momentensensorik unbekannt ist. In dieser Arbeit wird die nichtlineare modellbasierte Trajektorienfolgeregelung eines Roboters mit sechs pneumatischen Drehgelenken vorgestellt. Sie umfasst die Mechanik und Pneumatik sowie, im Gegensatz zum Stand der Technik, deren Verkopplung in einem zentralen Regler. Ausgehend vom dynamischen Modell des Gesamtsystems wird der Regler mittels Feedback-Linearisierung, einem Sonderfall der differentiellen Flachheit, hergeleitet. Die Regelung wird experimentell validiert und anhand der Messungen werden praktische Auswirkungen ihrer Struktur aufgezeigt.

The potential transformation of hexachlorocyclohexane isomers (HCHs) within tree trunks could have a significant impact on the use of phytoscreening. However, the transformation mechanisms of HCH in trunks particularly in growth rings are not yet well understood. Therefore, a field study on an HCH-contaminated field site was conducted to investigate the fate of HCH, particularly α-HCH in tree trunks using multielement compound-specific isotope analysis (ME-CSIA) and enantiomer fractionation. The results indicate that α-HCH was transformed, as evidenced by higher δ13C and δ37Cl values detected across different growth ring sections and in the bark compared to those in muck and soil. Remarkably, in the middle growth ring section, δ13C values of HCH were only marginally higher or comparable to those in muck, whereas δ37Cl values were higher than those of the muck, indicating a different transformation mechanism. Moreover, the δ37Cl values of β-HCH also increased in the tree trunks compared to those in soil and muck, implying a transformation of β-HCH. Additionally, dual-element isotope analysis revealed that there are different transformation mechanisms between the middle growth rings and other sections. Our findings suggest that the transformation of HCHs in trunks could bias quantitative phytoscreening approaches; however, ME-CISA offers an option to estimate the degradation extent.

This study systematically reviewed Australian literature to determine if an association exists between geospatial exposure to food outlets and diet, health or weight status. Recommendations for future research are provided. A systematic literature search was conducted in December 2021 using CINAHL Plus, PubMed and Web of Science databases. Data were extracted, as per the Preferred Reporting Items for Systematic Reviews and Meta‐Analyses guidelines. Study quality was assessed using an eight‐item checklist. A descriptive synthesis of study characteristics and findings was carried out, stratified via study outcomes. Of the 36 included articles, the majority were from Victoria (n = 19), involving adult participants (n = 30) and cross‐sectional in design (n = 27). Overall, associations were mainly null (nonsignificant) for diet (80%), weight status (75%) and health outcomes (90%). Significant findings were mixed with no positive trend with study quality. Six recommendations are suggested to address current knowledge gaps and limitations in the Australian evidence base: (1) Conduct research on different populations; (2) Employ robust study designs that can test the impact of change over time; (3) Improve the accuracy of food outlet data sources; (4) Improve food outlet geospatial exposure measures; (5) Improve measurement of outcome variables; and (6) Incorporate theoretical models into study design and data analysis. Improving the quality and consistency of research will be critical to informing locally relevant policy. Despite the present limitations in the evidence base, it is reasonable to assume that decisions to purchase and consume food are driven by availability and access. Thus, policy and planning aimed at improving the overall “healthiness” of the community food environment by increasing access to healthy food outlets is warranted to ensure that healthy options are easier choice for all.