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Usaha Mikro, Kecil, dan Menengah merupakan satu kekuatan ekonomi melalui kemampuannya untuk menyerap tenaga kerja. Salah satu kategori usaha yang memiliki peluang yang besar adalah jasa kecantikan karena jumlahnya masih sedikit, terutama di Tasikmalaya. Pandemi Covid-19 menjadi kendala utama bagi pelaku usaha yang memasarkan produk/jasanya secara langsung. Talita Care merupakan salah satu usaha bidang kecantikan yang masih melakukan pemasaran secara konvensional dan belum memiliki kompetensi untuk melakukan pemasaran secara digital. Karena itu diberikan program pendampingan kepada Talita Care untuk mengembangkan kemampuan Talita Care terutama dari sisi Pemasaran Digital. Penerapan Pemasaran Digital diangkat sebagai fokus pembahasan karena memiliki peran penting sebagai strategi promosi bagi produk Talita Care untuk semakin dikenal oleh masyarakat, bahkan setelah pandemi berakhir. Mengingat kondisi pandemi, program pendampingan dilakukan secara online dengan menggunakan media Zoom. Program ini berhasil membuka channel pemasaran baru bagi Talita Care, meningkatkan penjualan melalui platform digital serta meningkatkan kompetensi pemilik dan pegawai Talita Care dalam Pemasaran Digital.

The increase in the number of vehicles in Samarinda City occurs significantly every year this has the potential to decrease environmental quality, namely air pollution. People who are at risk of air pollution are street sweepers who work on the streets every day so that it can have an impact on health. Therefore, the purpose of this study was to determine the individual characteristics of lung function among street sweeping officers in Samarinda City. This research is a type of observational analytic study with a cross-sectional research design that has the aim of analyzing the risks to the consequences that are caused together. This research is included in the quantitative description. The research location was carried out along the protocol road in Samarinda City. The study population was street sweeping officers who were taken randomly amounting to 55 people. This study consisted of the dependent variable, namely lung function, and the independent variables were gender and year of service. Data analysis her use fisher’s exact. Data were collected using questionnaires and interviews, measuring lung function on street sweeping officers using a spirometer, while interviews were carried out to determine the sex and year of service of the officers while working as a street sweeper in Samarinda City. The results of the bivariate analysis of individual characteristics, namely between gender and lung function obtained p-value=0,674, while the bivariate results between a work period and lung function obtained p-value 0,219. There was no significant relationship between gender, work period, and lung function.

Pengelolaan sampah yang baik harus melibatkan partisipasi dari masyarakat untuk itu perlu pengenalan sejak dini dalam pengelolaan sampah sehingga pada saat dewasa sudah memahami manfaat dari pengelolaan sampah secara baik dan benar. Pengelolaan sampah mempunyai maksud untuk meningkatkan kesehatan masyarakat dan kualitas lingkungan serta menjadikan sampah sebagai sumber daya. Dari sudut pandang kesehatan lingkungan, pengelolaan sampah dipandang baik jika sampah tersebut tidak menjadi media berkembang biaknya bibit penyakit serta sampah tersebut tidak menjadi medium perantara menyebarluasnya suatu penyakit. Syarat lainnya yang harus dipenuhi, yaitu tidak mencemari udara, air dan tanah, tidak menimbulkan bau (tidak mengganggu nilai estetis), tidak menimbulkan kebakaran dan yang lainnya. Dari hal tersebut maka diperlukan pemahaman yang berkelanjutan dalam pendidikan kesehatan tentang pengelolaan sampah sejak dini. Tujuan Pengabdian Kepada Masyarakat ini untuk memberikan pengetahuan dan pemahaman tentang pengelolaan sampah sejak usia dini. Kegiatan yang dilakukan adalah 1) melakukan diskusi dengan guru untuk menggali informasi mengenai pengelolaan sampah yang sudah ada apakah sudah terpisah atau belum, 2) masalah apa yang dihadapi dalam mengelola sampah. Berdasarkan hasil kegiatan yang sudah dilaksanakan maka disimpulkan beberapa hal: 1) Pengelolaan sampah dikelola oleh seorang petugas kebersihan, 2) Tempat sampah masih bercampur antara sampah organik dan sampah anorganik, 3) Siswa/siswi SDN 015 Samarinda Ulu berpotensi untuk merubah perilaku mereka untuk membuang sampah sesuai dengan tempat dan jenis sampahnya, 4) Penyuluhan dan pendampingan pada saat proses kegiatan berjalan dengan lancar dan antusiasme dari siswa siswinya sangat tinggi. 5) sudah di tempatkan tempat sampah yang terpisah.

Sono molto affezionato ad Achille Mbembe, per una ragione incomprensibile che mi colpisce mentre leggo il suo nuovo libro, Brutalisme. Quest’autore camerunese mi aveva conquistato già nel 1992, quando ho letto il suo articolo The Banality of Power and the Aesthetics of Vulgarity in the Postcolony sulla rivista Public Culture.

Ruang publik merupakan ruang untuk melakukan kegiatan sosial, ekonomi, dan budaya. Selain ruang terbuka hijau, ruang sepanjang sungai juga mempunyai potensi untuk dijadikan sebagai sebagai ruang publik. Faktanya ruang sepanjang sungai hanya digunakan untuk permukiman liar dan tidak ada penyediaan ruang publik di dalamnya. Penelitian akan berfokus pada penentuan kriteria yang dibutuhkan untuk membentuk ruang publik di sekitar bantaran sungai dalam mendukung aksesibiltas dan peningkatan aktivitas. Teori yang akan digunakan ialah prinsip kawasan terintegrasi sungai (Charles A. McLaren - A Guide to Riverfront Development) dan teori Public Space oleh Stephen Carr dan Carmona. Tapak yang akan di analisis adalah ruang publik di Kawasan Kalijodo yang berbatasan langsung dengan air. Berdasarkan kedua teori yang digabungkan, kriteria yang akan digunakan dalam menganalisis objek studi adalah kenyamanan, aktivitas, sosiabilitas dan yang ditekankan ialah akses, meliputi titik akses pedestrian, tipe dan distribusi akses universal, dan prioritas pedestrian. Berdasarkan penelitian dapat disimpulkan akses secara fisikal sudah terpenuhi dengan adanya tangga dan jembatan penghubung dari sungai, namun harus mempertimbangkan akses secara visual, menambahkan program yang spesifik agar pemetaan merata dan ditunjang dengan vegetasi yang lebih rapat untuk mendukung kenyamanan.

Abstract Background The social gradient in disability pension is well recognized, however mechanisms accounting for the gradient are largely unknown. The aim of this study was to examine the association between occupational class and subsequent disability pension among middle-aged men and women, and to what extent work-related factors accounted for the association. Methods A subsample (N = 7031) of the population-based Hordaland Health Study (HUSK) conducted in 1997-99, provided self-reported information on health and work-related factors, and were grouped in four strata by Erikson, Goldthorpe and Portocareros occupational class scheme. The authors obtained follow-up data on disability pension by linking the health survey to national registries of benefit (FD-trygd). They employed Cox regression analysis and adjusted for gender, health (medical conditions, mental health, self-perceived health, somatic symptoms) and work-related factors (working hours, years in current occupation, physical demands, job demands, job control). Results A strong gradient in disability pension by occupational class was found. In the fully adjusted model the risk (hazard ratio) ranged from 1.41 (95% CI 0.84 to 2.33) in the routine non-manual class, 1.87 (95% CI 1.07 to 3.27) in the skilled manual class and 2.12 (95% CI 1.14 to 3.95) in the unskilled manual class, employing the administrator and professional class as reference. In the gender and health-adjusted model work-related factors mediated the impact of occupational class on subsequent disability pension with 5% in the routine non-manual class, 26% in the skilled manual class and 24% in the unskilled manual class. The impact of job control and physical demands was modest, and mainly seen among skilled and unskilled manual workers. Conclusions Workers in the skilled and unskilled manual classes had a substantial unexplained risk of disability pension. Work-related factors only had a moderate impact on the disability risk. Literature indicates an accumulation of hazards in the manual classes. This should be taken into account when interpreting the gradient in disability pension.

Abstract Background In unipolar, and bipolar affective disorders, there is a high risk of relapse that increases as the number of episodes increases. Naturalistic follow-up studies suggest that the progressive development of the diseases is not prevented with the present treatment modalities. It is not known whether centralised and specialised secondary care intervention initiated early after the onset of the diseases can prevent the progression and thereby improve the prognosis. Methods Two randomised clinical multi-centre trials comparing a centralised and specialised outpatient intervention program consisting of combined pharmacological and psychological intervention with standard decentralised psychiatric treatment. Patients discharged from their first, second, or third hospitalisation due to a manic episode or bipolar disorder (trial 1) or to a single depressive episode or recurrent depressive disorder (trial 2) were randomised. Central randomisations for both trials were stratified for the number of hospitalisations and treatment centre. The primary outcome measure for the two trials is time to re-hospitalisation with an affective episode. Discussion These trials are the first to evaluate the effect of a centralised and specialised intervention in patients with early severe affective disorders. The trials used a pragmatic design comparing a specialised mood disorder clinic intervention with decentralised, non-specialised standard psychiatric treatment. Trial Registration ClinicalTrials.gov: NCT00253071

Abstract Background The etiology of the neurogenerative disease multiple sclerosis (MS) is unknown. The leading hypotheses suggest that MS is the result of exposure of genetically susceptible individuals to certain environmental factor(s). Herpesviruses and human endogenous retroviruses (HERVs) represent potentially important factors in MS development. Herpesviruses can activate HERVs, and HERVs are activated in MS patients. Results Using flow cytometry, we have analyzed HERV-H Env and HERV-W Env epitope expression on the surface of PBMCs from MS patients with active and stable disease, and from control individuals. We have also analyzed serum antibody levels to the expressed HERV-H and HERV-W Env epitopes. We found a significantly higher expression of HERV-H and HERV-W Env epitopes on B cells and monocytes from patients with active MS compared with patients with stable MS or control individuals. Furthermore, patients with active disease had relatively higher numbers of B cells in the PBMC population, and higher antibody reactivities towards HERV-H Env and HERV-W Env epitopes. The higher antibody reactivities in sera from patients with active MS correlate with the higher levels of HERV-H Env and HERV-W Env expression on B cells and monocytes. We did not find such correlations for stable MS patients or for controls. Conclusion These findings indicate that both HERV-H Env and HERV-W Env are expressed in higher quantities on the surface of B cells and monocytes in patients with active MS, and that the expression of these proteins may be associated with exacerbation of the disease.

Abstract Background Many breast, pancreatic, colonic and non-small-cell lung carcinoma lines express CEACAM6 (NCA-90) and CEACAM5 (carcinoembryonic antigen, CEA), and antibodies to both can affect tumor cell growth in vitro and in vivo. Here, we compare both antigens as a function of histological phenotype in breast, pancreatic, lung, ovarian, and prostatic cancers, including patient-matched normal, primary tumor, and metastatic breast and colonic cancer specimens. Methods Antigen expression was determined by immunohistochemistry (IHC) using tissue microarrays with MN-15 and MN-3 antibodies targeting the A1B1- and N-domains of CEACAM6, respectively, and the MN-14 antibody targeting the A3B3 domain of CEACAM5. IHC was performed using avidin-biotin-diaminobenzide staining. The average score ± SD (0 = negative/8 = highest) for each histotype was recorded. Results For all tumors, the amount of CEACAM6 expressed was greater than that of CEACAM5, and reflected tumor histotype. In breast tumors, CEACAM6 was highest in papillary > infiltrating ductal > lobular > phyllodes; in pancreatic tumors, moderately-differentiated > well-differentiated > poorly-differentiated tumors; mucinous ovarian adenocarcinomas had almost 3-fold more CEACAM6 than serous ovarian adenocarcinomas; lung adenocarcinomas > squamous tumors; and liver metastases of colonic carcinoma > primary tumors = lymph nodes metastases > normal intestine. However, CEACAM6 expression was similar in prostate cancer and normal tissues. The amount of CEACAM6 in metastatic colon tumors found in liver was higher than in many primary colon tumors. In contrast, CEACAM6 immunostaining of lymph node metastases from breast, colon, or lung tumors was similar to the primary tumor. Conclusion CEACAM6 expression is elevated in many solid tumors, but variable as a function of histotype. Based on previous work demonstrating a role for CEACAM6 in tumor cell migration, invasion and adhesion, and formation of distant metastases (Blumenthal et al., Cancer Res 65: 8809–8817, 2005), it may be a promising target for antibody-based therapy.

Common half-cell measurements deliver oxygen reduction activities linked to the chosen scan rate, limiting their value for fundamental and comparative studies on platinum. Here we show a deconvolution of the intrinsic kinetics from the effect of surface oxygen on platinum. We find an electronic effect of the surface oxygen, substantiate a Tafel slope of ~120 mV/decade, obtain an exchange current density of 13 ± 4 µA/cm 2 , and an activity of 7 mA/cm 2 at 900 mV. Eventually, we broaden the scope of this analysis to the effects of surface rearrangement, alloying, and supported Pt nanoparticles, the latter providing insight into discrepancies between half-cell and fuel cell measurements. We find through computational methods that binding energies of intermediates would be weakened by the presence of highly coordinated oxygen atoms. Finally, we obtain a phenomenological rate equation for the oxygen reduction and evolution reaction, suggesting that both reactions follow a shared mechanism., (© 2024. The Author(s).)

For oxygen reduction reaction (ORR), the surface adsorption energies of O and OH* intermediates are key descriptors for catalytic activity. In this work, we investigate anion-substituted zirconia catalyst surfaces and determine that adsorption energies of O and OH* intermediates is governed by both structural and electronic effects. When the adsorption energies are not influenced by the structural effects of the catalyst surface, they exhibit a linear correlation with integrated crystal orbital Hamiltonian population (ICOHP) of the adsorbate-surface bond. The influence of structural effects, due to the re-optimisation slab geometry after adsorption of intermediate species, leads to stronger adsorption of intermediates. Our calculations show that there is a change in the bond order to accommodate the incoming adsorbate species which leads to stronger adsorption when both structural and electronic effects influence the adsorption phenomena. The insights into the catalyst-adsorbate interactions can guide the design of future ORR catalysts., (© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Misophonia, a heightened aversion to certain sounds, turns common cognitive and social exercises (e.g., paying attention during a lecture near a pen-clicking classmate, coexisting at the dinner table with a food-chomping relative) into challenging endeavors. How does exposure to triggering sounds impact cognitive and social judgments? We investigated this question in a sample of 65 participants (26 misophonia, 39 control) from the general population. In Phase 1, participants saw faces paired with auditory stimuli while completing a gender judgment task, then reported sound discomfort and identification. In Phase 2, participants saw these same faces with novel ones and reported face likeability and memory. For both oral and non-oral triggers, misophonic participants gave higher discomfort ratings than controls did-especially when identification was correct-and performed slower on the gender judgment. Misophonic participants rated lower likeability than controls did for faces they remembered with high discomfort sounds, and face memory was worse overall for faces originally paired with high discomfort sounds. Altogether, these results suggest that misophonic individuals show impairments on social and cognitive judgments if they must endure discomforting sounds. This experiment helps us better understand the day-to-day impact of misophonia and encourages usage of individualized triggers in future studies., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Hansen et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

People tend to employ suboptimal attention control strategies during visual search. Here we question why people are suboptimal, specifically investigating how knowledge of the optimal strategies and the time available to apply such strategies affect strategy use. We used the Adaptive Choice Visual Search (ACVS), a task designed to assess attentional control optimality. We used explicit strategy instructions to manipulate explicit strategy knowledge, and we used display previews to manipulate time to apply the strategies. In the first two experiments, the strategy instructions increased optimality. However, the preview manipulation did not significantly boost optimality for participants who did not receive strategy instruction. Finally, in Experiments 3A and 3B, we jointly manipulated preview and instruction with a larger sample size. Preview and instruction both produced significant main effects; furthermore, they interacted significantly, such that the beneficial effect of instructions emerged with greater preview time. Taken together, these results have important implications for understanding the strategic use of attentional control. Individuals with explicit knowledge of the optimal strategy are more likely to exploit relevant information in their visual environment, but only to the extent that they have the time to do so., (© 2024. The Author(s).)

Electrochemical experiments and theoretical calculations have shown that Pd-based metal hydrides can perform well for the CO 2 reduction reaction (CO 2 RR). Our previous work on doped-PdH showed that doping Ti and Nb into PdH can improve the CO 2 RR activity, suggesting that the Pd alloy hydrides with better performance are likely to be found in the Pd x Ti 1-x H y and Pd x Nb 1-x H y phase space. However, the vast compositional and structural space with different alloy hydride compositions and surface adsorbates, makes it intractable to screen out the stable and active Pd x M 1-x H y catalysts using density functional theory calculations. Herein, an active learning cluster expansion (ALCE) surrogate model equipped with Monte Carlo simulated annealing (MCSA), a CO* binding energy filter and a kinetic model are used to identify promising Pd x Ti 1-x H y and Pd x Nb 1-x H y catalysts with high stability and superior activity. Using our approach, we identify 24 stable and active candidates of Pd x Ti 1-x H y and 5 active candidates of Pd x Nb 1-x H y . Among these candidates, the Pd 0.23 Ti 0.77 H, Pd 0.19 Ti 0.81 H 0.94 , and Pd 0.17 Nb 0.83 H 0.25 are predicted to display current densities of approximately 5.1, 5.1 and 4.6 μA cm -2 at -0.5 V overpotential, respectively, which are significantly higher than that of PdH at 3.7 μA cm -2 ., (© 2023 Wiley‐VCH GmbH.)

Palladium (Pd) hydride-based catalysts have been reported to have excellent performance in the CO 2 reduction reaction (CO 2 RR) and hydrogen evolution reaction (HER). Our previous work on doped PdH and Pd alloy hydrides showed that Ti-doped and Ti-alloyed Pd hydrides could improve the performance of the CO 2 reduction reaction compared with pure Pd hydride. Compositions and chemical orderings of the surfaces with only one adsorbate under certain reaction conditions are linked to their stability, activity, and selectivity toward the CO 2 RR and HER, as shown in our previous work. In fact, various coverages, types, and mixtures of the adsorbates, as well as state variables such as temperature, pressure, applied potential, and chemical potential, could impact their stability, activity, and selectivity. However, these factors are usually fixed at common values to reduce the complexity of the structures and the complexity of the reaction conditions in most theoretical work. To address the complexities above and the huge search space, we apply a deep learning-assisted multitasking genetic algorithm to screen for Pd x Ti 1- x H y surfaces containing multiple adsorbates for CO 2 RR under different reaction conditions. The ensemble deep learning model can greatly speed up the structure relaxations and retain a high accuracy and low uncertainty of the energy and forces. The multitasking genetic algorithm simultaneously finds globally stable surface structures under each reaction condition. Finally, 23 stable structures are screened out under different reaction conditions. Among these, Pd 0.56 Ti 0.44 H 1.06 + 25%CO, Pd 0.31 Ti 0.69 H 1.25 + 50%CO, Pd 0.31 Ti 0.69 H 1.25 + 25%CO, and Pd 0.88 Ti 0.12 H 1.06 + 25%CO are found to be very active for CO 2 RR and suitable to generate syngas consisting of CO and H 2 .

Molecular understanding of the solid-liquid interface is challenging but essential to elucidate the role of the environment on the kinetics of electrochemical reactions. Alkali metal cations (M + ), as a vital component at the interface, are found to be necessary for the initiation of carbon dioxide reduction reaction (CO 2 RR) on coinage metals, and the activity and selectivity of CO 2 RR could be further enhanced with the cation changing from Li + to Cs + , while the underlying mechanisms are not well understood. Herein, using ab initio molecular dynamics simulations with explicit solvation and enhanced sampling methods, we systematically investigate the role of M + in CO 2 RR on Cu surface. A monotonically decreasing CO 2 activation barrier is obtained from Li + to Cs + , which is attributed to the different coordination abilities of M + with *CO 2 . Furthermore, we show that the competing hydrogen evolution reaction must be considered simultaneously to understand the crucial role of alkali metal cations in CO 2 RR on Cu surfaces, where H + is repelled from the interface and constrained by M + . Our results provide significant insights into the design of electrochemical environments and highlight the importance of explicitly including the solvation and competing reactions in theoretical simulations of CO 2 RR., (© 2024. The Author(s).)

The underlying mechanism of cation effects on CO 2 RR remains debated. Herein, we study cation effects by simulating both outer-sphere electron transfer (OS-ET) and inner-sphere electron transfer (IS-ET) pathways during CO 2 RR via constrained density functional theory molecular dynamics (cDFT-MD) and slow-growth DFT-MD (SG-DFT-MD), respectively. Our results show without any cations, only OS-ET is feasible with a barrier of 1.21 eV. In the presence of K + (Li + ), OS-ET shows a very high barrier of 2.93 eV (4.15 eV) thus being prohibited. However, cations promote CO 2 activation through IS-ET with the barrier of only 0.61 eV (K + ) and 0.91 eV (Li + ), generating the key intermediate (adsorbed CO[Formula: see text]). Without cations, CO 2 -to-CO[Formula: see text](ads) conversion cannot proceed. Our findings reveal cation effects arise from short-range Coulomb interactions with reaction intermediates. These results disclose that cations modulate the inner- and outer-sphere pathways of CO 2 RR, offering substantial insights on the cation specificity in the initial CO 2 RR steps., (© 2023. The Author(s).)

The application of ab initio molecular dynamics (AIMD) for the explicit modeling of reactions at solid-liquid interfaces in electrochemical energy conversion systems like batteries and fuel cells can provide new understandings towards reaction mechanisms. However, its prohibitive computational cost severely restricts the time- and length-scales of AIMD. Equivariant graph neural network (GNN) based accurate surrogate potentials can accelerate the speed of performing molecular dynamics after learning on representative structures in a data efficient manner. In this study, we combined uncertainty-aware GNN potentials and enhanced sampling to investigate the reactive process of the oxygen reduction reaction (ORR) at an Au(100)-water interface. By using a well-established active learning framework based on CUR matrix decomposition, we can evenly sample equilibrium structures from MD simulations and non-equilibrium reaction intermediates that are rarely visited during the reaction. The trained GNNs have shown exceptional performance in terms of force prediction accuracy, the ability to reproduce structural properties, and low uncertainties when performing MD and metadynamics simulations. Furthermore, the collective variables employed in this work enabled the automatic search of reaction pathways and provide a detailed understanding towards the ORR reaction mechanism on Au(100). Our simulations identified the associative reaction mechanism without the presence of *O and a low reaction barrier of 0.3 eV, which is in agreement with experimental findings. The methodology employed in this study can pave the way for modeling complex chemical reactions at electrochemical interfaces with an explicit solvent under ambient conditions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We present a computational study of the energetics and mechanisms of oxidation of Pt-Mn systems. We use slab models and simulate the oxidation process over the most stable (111) facet at a given Pt 2 Mn composition to make the problem computationally affordable, and combine Density-Functional Theory (DFT) with neural network potentials and metadynamics simulations to accelerate the mechanistic search. We find, first, that Mn has a strong tendency to alloy with Pt. This tendency is optimally realized when Pt and Mn are mixed in the bulk, but, at a composition in which the Mn content is high enough such as for Pt 2 Mn, Mn atoms will also be found in the surface outmost layer. These surface Mn atoms can dissociate O 2 and generate MnO x species, transforming the surface-alloyed Mn atoms into MnO x surface oxide structures supported on a metallic framework in which one or more vacancy sites are simultaneously created. The thus-formed vacancies promote the successive steps of the oxidation process: the vacancy sites can be filled by surface oxygen atoms, which can then interact with Mn atoms in deeper layers, or subsurface Mn atoms can intercalate into interstitial sites. Both these steps facilitate the extraction of further bulk Mn atoms into MnO x oxide surface structures, and thus the progress of the oxidation process, with typical rate-determining energy barriers in the range 0.9-1.0 eV.

Electrochemical CO 2 reduction reaction (CO 2 RR) is a promising technology for the clean energy economy. Numerous efforts have been devoted to enhancing the mechanistic understanding of CO 2 RR from both experimental and theoretical studies. Electrolyte ions are critical for the CO 2 RR; however, the role of alkali metal cations is highly controversial, and a complete free energy diagram of CO 2 RR at Au-water interfaces is still missing. Here, we provide a systematic mechanism study toward CO 2 RR via ab initio molecular dynamics simulations integrated with the slow-growth sampling (SG-AIMD) method. By using the SG-AIMD approach, we demonstrate that CO 2 RR is facile at the inner-sphere interface in the presence of K cations, which promote the CO 2 activation with the free energy barrier of only 0.66 eV. Furthermore, the competitive hydrogen evolution reaction (HER) is inhibited by the interfacial cations with the induced kinetic blockage effect, where the rate-limiting Volmer step shows a much higher energy barrier (1.27 eV). Eventually, a comprehensive free energy diagram including both kinetics and thermodynamics of the CO 2 RR to CO and the HER at the electrochemical interface is derived, which illustrates the critical role of cations on the overall performance of CO 2 electroreduction by facilitating CO 2 adsorption while suppressing the hydrogen evolution at the same time.

Transition-metal-mediated dinitrogen fixation has been intensively investigated. The employment of main group elements for this vital reaction has recently sparked interest because of new dinitrogen reaction chemistry. We report ammonia synthesis via a chemical looping process mediated by a transition-metal-free barium hydride (BaH 2 ). Experimental and computational studies reveal that the introduction of hydrogen vacancies is essential for creating multiple coordinatively unsaturated Ba sites for N 2 activation. The adjacent lattice hydridic hydrogen (H - ) then undergoes both reductive elimination and reductive protonation to convert N 2 to NH x . The ammonia production rate supports this hydride-vacancy mechanism via a chemical looping route that far exceeds that of a catalytic process. The BaH 2 -mediated chemical looping process has prospects in future technologies for ammonia synthesis using transition-metal-free materials., (© 2022 Wiley-VCH GmbH.)

Misophonia, an extreme aversion to certain environmental sounds, is a highly prevalent yet understudied condition plaguing roughly 20% of the general population. Although neuroimaging research on misophonia is scant, recent work showing higher resting-state functional connectivity (rs-fMRI) between auditory cortex and orofacial motor cortex in misophonia vs. controls has led researchers to speculate that misophonia is caused by orofacial mirror neurons. Since orofacial motor cortex was defined using rs-fMRI, we attempted to theoretically replicate these findings using orofacial cortex defined by task-based fMRI instead. Further, given our recent work showing that a wide variety of sounds can be triggering (i.e., not just oral/nasal sounds), we investigated whether there is any neural evidence for misophonic aversion to non-orofacial stimuli. Sampling 19 adults with varying misophonia from the community, we collected resting state data and an fMRI task involving phoneme articulation and finger-tapping. We first defined "orofacial" cortex in each participant using rs-fMRI as done previously, producing what we call resting-state regions of interest (rsROIs). Additionally, we functionally defined regions (fROIs) representing "orofacial" or "finger" cortex using phoneme or finger-tapping activation from the fMRI task, respectively. To investigate the motor specificity of connectivity differences, we subdivided the rsROIs and fROIs into separate sensorimotor areas based on their overlap with two common atlases. We then calculated rs-fMRI between each rsROI/fROI and a priori non-sensorimotor ROIs. We found increased connectivity in mild misophonia between rsROIs and both auditory cortex and insula, theoretically replicating previous results, with differences extending across multiple sensorimotor regions. However, the orofacial task-based fROIs did not show this pattern, suggesting the "orofacial" cortex described previously was not capturing true orofacial cortex; in fact, using task-based fMRI evidence, we find no selectivity to orofacial action in these previously described "orofacial" regions. Instead, we observed higher connectivity between finger fROIs and insula in mild misophonia, demonstrating neural evidence for non-orofacial triggers. These results provide support for a neural representation of misophonia beyond merely an orofacial/motor origin, leading to important implications for the conceptualization and treatment of misophonia., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Hansen, Stefancin, Leber and Saygin.)

PdH-based catalysts hold promise for both CO 2 reduction to CO and the hydrogen evolution reaction. Density functional theory is used to systematically screen for stability, activity, and selectivity of transition metal dopants in PdH. The transition metal elements Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Ag, Cd, Hf, Ta, W, and Re are doped into PdH(111) surface with six different doping configurations: single, dimer, triangle, parallelogram, island, and overlayer. We find that several dopants, such as Ti and Nb, have excellent predicted catalytic activity and CO 2 selectivity compared to the pure PdH hydride. In addition, they display good stability due to their negative doping formation energy. The improved performance can be assigned to reaction intermediates forming two bonds consisting of one C-Metal and one O-Metal bond on the PdH surface, which break the scaling relations of intermediates, and thus have stronger HOCO* binding facilitating CO 2 activation., (© 2022 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The interactions between liquid water and hydroxyl species on Pt(111) surfaces have been intensely investigated due to their importance to fuel cell electrocatalysis. Here we present a molecular dynamics study of their structure and energetics using an ensemble of neural network potentials, which allow us to obtain unprecedented statistical sampling. We first study the energetics of hydroxyl formation, where we find a near-linear adsorption energy profile, which exhibits a soft and gradual increase in the differential adsorption energy at high hydroxyl coverages. This is strikingly different from the predictions of the conventional bilayer model, which displays a kink at 1/3ML OH coverage indicating a sizeable jump in differential adsorption energy, but within the statistical uncertainty of previously reported ab initio molecular dynamics studies. We then analyze the structure of the interface, where we provide evidence for the water-OH/Pt(111) interface being hydrophobic at high hydroxyl coverages. We furthermore explain the observed adsorption energetics by analyzing the hydrogen bonding in the water-hydroxyl adlayers, where we argue that the increase in differential adsorption energy at high OH coverage can be explained by a reduction in the number of hydrogen bonds from the adsorbed water molecules to the hydroxyls.

Objectives: Misophonia is a highly prevalent yet understudied condition characterized by aversion toward particular environmental sounds. Oral/nasal sounds (e.g., chewing, breathing) have been the focus of research, but variable experiences warrant an objective investigation. Experiment 1 asked whether human-produced oral/nasal sounds were more aversive than human-produced nonoral/nasal sounds and non-human/nature sounds. Experiment 2 additionally asked whether machine-learning algorithms could predict the presence and severity of misophonia., Method: Sounds were presented to individuals with misophonia (Exp.1: N = 48, Exp.2: N = 45) and members of the general population (Exp.1: N = 39, Exp.2: N = 61). Aversiveness ratings to each sound were self-reported., Results: Sounds from all three source categories-not just oral/nasal sounds-were rated as significantly more aversive to individuals with misophonia than controls. Further, modeling all sources classified misophonia with 89% accuracy and significantly predicted misophonia severity (r = 0.75)., Conclusions: Misophonia should be conceptualized as more than an aversion to oral/nasal sounds, which has implications for future diagnostics and experimental consistency moving forward., (© 2021 Wiley Periodicals LLC.)

The electrochemical reduction of CO 2 into valuable chemicals under mild conditions has become a promising technology for energy storage and conversion in the past few years, receiving much attention from theoretical researchers investigating the reaction mechanisms. However, most of the previous simulations are related to the key intermediates of *COOH and *CO using the computational hydrogen electrode approach under vacuum conditions, and the details of the CO 2 activation are usually ignored due to the model simplicity. Here, we study the CO 2 activation at the Au-water interfaces by considering the dynamics of an explicit water solvent, where both regular ab initio molecular dynamics and constrained ab initio molecular dynamics simulations are carried out to explore the CO 2 adsorption/desorption reactions from the atomic level. By introducing K + cations into Au(110)-water interfacial models, an electrochemical environment under reducing potentials is constructed, where the reaction free energy (0.26 eV) and activation energy (0.61 eV) are obtained for CO 2 adsorption based on the thermodynamic integration. Moreover, the Bader charge analysis demonstrates that CO 2 adsorption is activated by the first-electron transfer, forming the adsorbed CO 2 - anion initiating the overall catalytic reaction.

Graphite felt is a widely used electrode material for vanadium redox flow batteries. Electrode activation leads to the functionalization of the graphite surface with epoxy, OH, C=O, and COOH oxygenic groups and changes the carbon surface morphology and electronic structure, thereby improving the electrode's electroactivity relative to the untreated graphite. In this study, density functional theory (DFT) calculations are conducted to evaluate functionalization's contribution towards the positive half-cell reaction of the vanadium redox flow battery. The DFT calculations show that oxygenic groups improve the graphite felt's affinity towards the VO 2+ /VO 2 + redox couple in the following order: C=O>COOH>OH> basal plane. Projected density-of-states (PDOS) calculations show that these groups increase the electrode's sp 3 hybridization in the same order, indicating that the increase in sp 3 hybridization is responsible for the improved electroactivity, whereas the oxygenic groups' presence is responsible for this sp 3 increment. These insights can aid the selection of activation processes and optimization of their parameters., (© 2021 Wiley-VCH GmbH.)

In this study, we use density functional theory to investigate the catalytic activity of graphene (G), single vacancy defective graphene (G SV ), quaternary N-doped graphene (NG Q ), and pyridinic N-doped graphene (NG py , 3NG py , and 4NG py ) on Co(0001) substrate for an oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). The results show pyridinic N-doped graphene on a Co support exhibited better performance than the NG Q on a Co support and free-standing systems. According to the results, ORR intermediates (*OOH, *O, and *OH) become more stable due to the presence of a Co substrate. The single pyridinic (3NG py ) layer placed on Co(0001) is the most active site. The overpotential for Co/3NG py is rather higher compared to pure Pt(111) catalyst (0.65 V). Therefore, pyridinic N-doped graphene with a cobalt support could be a promising strategy to enhance the ORR activity of N-doped graphene in PEMFCs.

What determines the functional organization of cortex? One hypothesis is that innate connectivity patterns, either structural or functional connectivity, set up a scaffold upon which functional specialization can later take place. We tested this hypothesis by asking whether the visual word form area (VWFA), an experience-driven region, was already functionally connected to proto language networks in neonates scanned within one week of birth. Using the data from the Human Connectone Project (HCP) and the Developing Human Connectome Project (dHCP), we calculated intrinsic functional connectivity during resting-state functional magnetic resonance imaging (fMRI), and found that neonates showed similar functional connectivity patterns to adults. We observed that (1) language regions connected more strongly with the putative VWFA than other adjacent ventral visual regions that also show foveal bias, and (2) the VWFA connected more strongly with frontotemporal language regions than with regions adjacent to these language regions. These data suggest that the location of the VWFA is earmarked at birth due to its connectivity with the language network, providing evidence that innate connectivity instructs the later refinement of cortex.

The amygdala, a subcortical structure known for social and emotional processing, consists of multiple subnuclei with unique functions and connectivity patterns. Tracer studies in adult macaques have shown that the basolateral subnuclei differentially connect to parts of visual cortex, with stronger connections to anterior regions and weaker connections to posterior regions; infant macaques show robust connectivity even with posterior visual regions. Do these developmental differences also exist in the human amygdala, and are there specific functional regions that undergo the most pronounced developmental changes in their connections with the amygdala? To address these questions, we explored the functional connectivity (from resting-state fMRI data) of the basolateral amygdala to occipitotemporal cortex in human neonates scanned within one week of life and compared the connectivity patterns to those observed in young adults. Specifically, we calculated amygdala connectivity to anterior-posterior gradients of the anatomically-defined occipitotemporal cortex, and also to putative occipitotemporal functional parcels, including primary and high-level visual and auditory cortices (V1, A1, face, scene, object, body, high-level auditory regions). Results showed a decreasing gradient of functional connectivity to the occipitotemporal cortex in adults-similar to the gradient seen in macaque tracer studies-but no such gradient was observed in neonates. Further, adults had stronger connections to high-level functional regions associated with face, body, and object processing, and weaker connections to primary sensory regions (i.e., A1, V1), whereas neonates showed the same amount of connectivity to primary and high-level sensory regions. Overall, these results show that functional connectivity between the amygdala and occipitotemporal cortex is not yet differentiated in neonates, suggesting a role of maturation and experience in shaping these connections later in life., Competing Interests: The authors have declared that no competing interests exist.

The development of an efficient electrocatalyst for the oxygen reduction reaction (ORR) is essential for the commercialization of fuel-cell technologies. Iron carbide encapsulated in N-doped graphene (NG/Fe 3 C) has been recognized recently as a promising ORR catalyst. In this study, the stability and catalytic activity of N-doped graphene supported on metal-iron carbide (NG/M_Fe 3 C) toward the ORR are investigated by using DFT calculations. The NG/M_Fe 3 C heterostructure is modeled by substituting Fe atoms in the Fe 3 C substrate near the NG/Fe 3 C interface by metal atoms M (M=Cr-Mn, Co-Zn, Nb-Mo, Ta-W). The calculations show that the introduction of the metal atoms M alters the work function of the overlayer N-doped graphene, which is found to correlate with the binding strength of the ORR intermediates. The introduction of Ni or Co atoms at the interface improves the ORR activity of the NG/Fe 3 C and stabilizes the heterostructure. The ORR activity increases as the concentration of Ni or Co atoms near the interface increases, and the stable heterostructure is available in a wide range of substituted concentrations. These results suggest approaches to improve the ORR activity of NG/Fe 3 C catalysts., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Electrochemical reaction rates are sensitive to interactions between electrolyte cations and adsorbed reaction intermediates, e.g., cation-*OH interactions in the oxygen reduction reaction on platinum. Here, we calculate the free energy interaction between adsorbed *OH and K+/Li+ situated at the liquid water-Pt(111) interface using ab initio molecular dynamics (AIMD) and metadynamics. Li+ stabilizes *OH by 0.1 ± 0.1 eV and K+ destabilizes *OH by 0.1 ± 0.1 eV, in qualitative agreement with experimental cyclic voltammogram (CV) measurements. In contrast, the internal energy of *OH is stabilized by 0.3 eV and 0.4 eV for Li+ and K+, respectively. This demonstrates that entropy significantly destabilizes cation-*OH interactions and is vital in order to understand even the relative influence of cations at interfaces.

Metal and nitrogen codoped carbons (M-N/Cs) have emerged as promising alternatives to platinum-based catalysts for the oxygen reduction reaction (ORR). DFT calculations are used to investigate the adsorption of anions and impurities from the electrolyte on the active site, modeled as an M-N 4 motif embedded in a planar carbon sheet (M=Cr, Mn, Fe, Co). The two-dimensional catalyst structure implies that each metal atom has two potential active sites, one on each side of the sheet. Adsorption of anions or impurities on both sites results in poisoning, but adsorption on one of the sites leads to a modified ORR activity on the remaining site. The calculated adsorption energies show that a number of species adsorb only on one of the two sites under realistic experimental conditions. Furthermore, a few of these adsorbates modify the adsorption energies of the ORR intermediates on the remaining site, in such a way that the limiting potential is improved., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

There are many strategies we can use to control attention when approaching a visual search task, but some are more effective than others. How do we choose the most optimal strategy? We have proposed that individuals must appraise the stimulus environment, taking in relevant statistical information about task-relevant features. In the present experiments, we examined whether interfering with the appraisal process via a secondary task decreases participants' use of the optimal strategy. We used a modified version of the Adaptive Choice Visual Search paradigm whereby individuals can freely search for either of two targets on every trial. Each search display was preceded by a colored environmental preview, offering participants time to appraise the display and determine which target would be more optimal to search for. On some blocks, participants also completed a secondary task - a central line-length judgment - either before or during this colored preview. We found that participants were significantly less likely to search optimally when the line task occurred during the colored preview than when it occurred beforehand or was absent. Insofar as the secondary task disrupts an individual's ability to engage in appraisal, these results support the need for such an appraisal mechanism in the optimal choice of attentional control settings.

The liquid water-Pt(111) interface is studied with constant temperature ab initio molecular dynamics to explore the importance of liquid water dynamics of catalytic reactions such as the oxygen reduction reaction in PEM fuel cells. The structure and energetics of hydroxyls formed at the liquid water-Pt(111) interface are found to be significantly different from those of the hydroxyl formed on a bare Pt(111) surface and the hydroxyl formed on a Pt(111) surface with a static water layer. We identify 1/12 ML *OH, 5/12 ML *OH and 2/3 ML *OH as particularly stable hydroxyl coverages in highly dynamic liquid water environments, which - contrary to static water-hydroxyl models - contain adjacent uncovered Pt sites. Atomic surface oxygen is found to be unstable in the presence of liquid water, in contrast to static atomic level simulations. These results give an improved understanding of hydroxide and surface oxide formation from Pt(111) cyclic voltammetry and allow us to draw detailed connections between the electrostatic potential and the interface structure. The study of hydrogen adsorption at the liquid water-Pt(111) interface finds competitive adsorption between the adsorbed hydrogen atoms and water molecules. This does not adhere with experimental observations, and this indicates that the Pt(111) surface has to be negatively charged for a correct description of the liquid water-Pt(111) interface at potentials where hydrogen adsorption occurs.

Zinc-air batteries offer the potential of low-cost energy storage with high specific energy, but at present secondary Zn-air batteries suffer from poor cyclability. To develop economically viable secondary Zn-air batteries, several properties need to be improved: choking of the cathode, catalyzing the oxygen evolution and reduction reactions, limiting dendrite formation and suppressing the hydrogen evolution reaction (HER). Understanding and alleviating HER at the negative electrode in a secondary Zn-air battery is a substantial challenge, for which it is necessary to combine computational and experimental research. Here, we combine differential electrochemical mass spectrometry (DEMS) and density functional theory (DFT) calculations to investigate the fundamental role and stability when cycling in the presence of selected beneficial additives, that is, In and Bi, and Ag as a potentially unfavorable additive. We show that both In and Bi have the desired property for a secondary battery, that is, upon recharging they will remain on the surface, thereby retaining the beneficial effects on Zn dissolution and suppression of HER. This is confirmed by DEMS, where it is observed that In reduces HER and Bi affects the discharge potential beneficially compared to a battery without additives. Using a simple procedure based on adsorption energies calculated with DFT, it is found that Ag suppresses OH adsorption, but, unlike In and Bi, it does not hinder HER. Finally, it is shown that mixing In and Bi is beneficial compared to the additives by themselves as it improves the electrochemical performance and cyclic stability of the secondary Zn-air battery., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Dijksterhuis and van Knippenberg (1998) reported that participants primed with a category associated with intelligence ("professor") subsequently performed 13% better on a trivia test than participants primed with a category associated with a lack of intelligence ("soccer hooligans"). In two unpublished replications of this study designed to verify the appropriate testing procedures, Dijksterhuis, van Knippenberg, and Holland observed a smaller difference between conditions (2%-3%) as well as a gender difference: Men showed the effect (9.3% and 7.6%), but women did not (0.3% and -0.3%). The procedure used in those replications served as the basis for this multilab Registered Replication Report. A total of 40 laboratories collected data for this project, and 23 of these laboratories met all inclusion criteria. Here we report the meta-analytic results for those 23 direct replications (total N = 4,493), which tested whether performance on a 30-item general-knowledge trivia task differed between these two priming conditions (results of supplementary analyses of the data from all 40 labs, N = 6,454, are also reported). We observed no overall difference in trivia performance between participants primed with the "professor" category and those primed with the "hooligan" category (0.14%) and no moderation by gender.

The CO oxidation reaction on single 3d-transition metal catalytic sites in experimentally realized tetracyanoquinodimethane (TM-TCNQ) monolayers (TM = Sc-Zn) is systematically investigated by means of first-principles calculations. Considering the stabilities, adsorption characteristics and thermodynamics of all the ten candidates (Sc-Zn), Sc-TCNQ is found to display the lowest activation energies and yield the highest catalytic activity for room temperature CO oxidation. Exploring the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms, we find that the rate-limiting step of CO oxidation catalyzed by Sc-TCNQ (CO + O 2 * → OOCO*) can follow the LH mechanism with free energy barriers as low as 0.73 eV at 300 K. The second step of CO + O* → CO 2 can occur with rather small energy barriers via either LH or ER mechanisms. The high activity of Sc-TCNQ can be attributed to its unique structural and electronic features by possessing high stability, optimum adsorption energies with adsorbates, and fast reaction kinetics. These results have significant implications for the synthesis of two-dimensional single atom catalysis for CO oxidation with low-cost and high activity at low temperature.

Minimizing energy and materials costs for driving the oxygen evolution reaction (OER) is paramount for the commercialization of water electrolysis cells and rechargeable metal-air batteries. Structural stability, catalytic activity, and electronic conductivity of pure and doped α-MnO 2 for the OER are studied using density functional theory calculations. As model surfaces, we investigate the (110) and (100) facets, on which three possible active sites are identified: a coordination unsaturated, a bridge, and a bulk site. For pure and Cr-, Fe-, Co-, Ni-, Cu-, Zn-, Cd-, Mg-, Al-, Ga-, In-, Sc-, Ru-, Rh-, Ir-, Pd-, Pt-, Ti-, Zr-, Nb-, and Sn-doped α-MnO 2 , the preferred valence at each site is imposed by adding/subtracting electron donors (hydrogen atoms) and electron acceptors (hydroxy groups). From a subset of stable dopants, Pd-doped α-MnO 2 is identified as the best catalyst and the only material that can outperform pristine α-MnO 2 . Different approaches to increase the bulk electron conductivity of semiconducting α-MnO 2 are discussed., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Ce 4+ /Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.Solid-state entropy of reduction increases the thermodynamic efficiency of ceria for two-step thermochemical water splitting. Here, the authors report a large and different source of entropy, the onsite electronic configurational entropy arising from coupling between orbital and spin angular momenta in f orbitals.

A detailed understanding of the electrochemical reduction of CO 2 into liquid fuels on rutile metal oxide surfaces is developed by using DFT calculations. We consider oxide overlayer structures on RuO 2 (1 1 0) surfaces as model catalysts to elucidate the trends and limitations in the CO 2 reduction reaction (CO2RR) based on thermodynamic analysis. We aim to specify the requirements for CO2RR catalysts to establish adsorbate scaling relations and use these to derive activity volcanoes. Computational results show that the OH* binding free energy is a good descriptor of the thermodynamic limitations and it defines the left leg of the activity volcano for CO2RR. HCOOH* is a key intermediate for products formed through further reduction, for example, methanediol, methanol, and methane. The surfaces that do not bind HCOOH* are selective towards formic acid (HCOOH) production, but hydrogen evolution limits their suitability. We determine the ideal binding free energy for H* and OH* to facilitate selective CO2RR over H 2 /CO evolution to be ΔG B [H]>0.5 eV and -0.5 eV<ΔG B [OH]<0.1 eV. The Re-containing overlayers considered in this work display excellent promise for selectivity, although they are active at a highly reducing potential., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ternary Pt-Au-M (M = 3d transition metal) nanoparticles show reduced OH adsorption energies and improved activity for the oxygen reduction reaction (ORR) compared to pure Pt nanoparticles, as obtained by density functional theory. The strain and ligand effects in nanoparticles are decoupled and correlated with the extended Pt(111) surface for benchmarking. The ternary metal in the core allows for tuning the catalytic activity through strain effects. Pt-Au-M for M = Cr, Mn, Co, Cu, Zn nanoparticles are of particular interest as they exhibit an optimal contribution of strain, ligand effects and stability. Good agreement is found with experimental studies showing increased activity of Pt-Au-Fe/Ni nanoparticles, and mid to late 3d transition metals are predicted to exhibit enhance activity and stability with respect to pure Pt nanoparticles.

South Texas currently has the highest incidence of hepatocellular carcinoma (HCC) in the United States, a disease that disproportionately affects Latino populations in the region. Aflatoxin B1 (AFB1) is a potent liver carcinogen that has been shown to be present in a variety of foods in the United States, including corn and corn products. Importantly, it is a dietary risk factor contributing to a higher incidence of HCC in populations frequently consuming AFB1-contaminated diets. In a randomised double-blind placebo controlled trial, we evaluated the effects of a 3-month administration of ACCS100 (refined calcium montmorillonite clay) on serum AFB1-lysine adduct (AFB-Lys) level and serum biochemistry in 234 healthy men and women residing in Bexar and Medina counties, Texas. Participants recruited from 2012 to 2014 received either a placebo, 1.5 g or 3 g ACCS100 each day for 3 months, and no treatment during the fourth month. Adverse event rates were similar across treatment groups and no significant differences were observed for serum biochemistry and haematology parameters. Differences in levels of AFB-Lys at 1, 3 and 4 months were compared between placebo and active treatment groups. Although serum AFB-Lys levels were decreased by month 3 for both treatment groups, the low dose was the only treatment that was significant (p = 0.0005). In conclusion, the observed effect in the low-dose treatment group suggests that the use of ACCS100 may be a viable strategy to reduce dietary AFB1 bioavailability during aflatoxin outbreaks and potentially in populations chronically exposed to this carcinogen., Competing Interests: Statement No potential conflict of interest was reported by the authors.

We use density functional theory to study the reduction of CO2 and CO to hydrocarbons through a formyl pathway on (111) and (211) facets of L12 alloys with an A3B composition. We find that several alloys may reduce the thermodynamic overpotential for CO reduction by more than 0.2 V compared to a copper step, however, these alloys are most often rather unstable in aqueous environment or have low alloy formation energies and may be susceptible to segregation destroying the active sites. Strategies to improve alloy stability against corrosion or segregation would likely be needed in order to realize the full potential of these alloys.

Introduction: The outcomes and complications following surgical treatment of tibial plateau fractures have been widely reported. The objective of this study was to evaluate the quality of life (QoL), functional and radiological outcomes after lateral tibial plateau fractures, Arbeitsgemeinschaft für Osteosynthesefragen (AO) type 41-B2 and B3, treated with minimally invasive bone tamp reduction, allograft and percutaneous screw fixation., Methods: This study was a cross-sectional study and a retrospective review and clinical evaluation of patients treated with minimally invasive bone tamp reduction, allograft and percutaneous screw fixation after lateral tibial plateau fractures between 2005 and 2010. The patients completed a clinical examination, Knee Injury and Osteoarthritis Outcome Score (KOOS) and a questionnaire for evaluation of QoL (Eq5D-5L)., Results: A total of 28 patients agreed to participate (71%). The mean follow-up time was 2.5 years. Maintained anatomical joint reduction and alignment was achieved in 23 cases. The mean Eq5D-5L index was 0.850. The mean KOOS scores were: pain = 79.9, ADL = 80.8, symptoms = 73.0, QoL = 61.3 and sport = 54.4. Compared with Eq5D-5L reference norms, patients did not report significantly lower scores. Compared with a KOOS reference group, patients reported significantly lower KOOS scores in three subscales., Conclusions: Tibial plateau fractures AO type 41-B2 and 41-B3 treated with minimally invasive bone tamp reduction, allograft and percutaneous screw fixation showed a high rate of anatomical reduction (82%), a low rate of complications (3.5%) and a high level of satisfactory patient-reported QoL., Funding: none., Trial Registration: not relevant.

Using a DFT-based genetic algorithm (GA) approach, we have determined the most stable structure and stoichiometry of a 309-atom icosahedral AuCu nanoalloy, for potential use as an electrocatalyst for CO2 reduction. The identified core-shell nano-particle consists of a copper core interspersed with gold atoms having only copper neighbors and a gold surface with a few copper atoms in the terraces. We also present an adsorbate-dependent correction scheme, which enables an accurate determination of adsorption energies using a computationally fast, localized LCAO-basis set. These show that it is possible to use the LCAO mode to obtain a realistic estimate of the molecular chemisorption energy for systems where the computation in normal grid mode is not computationally feasible. These corrections are employed when calculating adsorption energies on the Cu, Au and most stable mixed particles. This shows that the mixed Cu135@Au174 core-shell nanoalloy has a similar adsorption energy, for the most favorable site, as a pure gold nano-particle. Cu, however, has the effect of stabilizing the icosahedral structure because Au particles are easily distorted when adding adsorbates.