Browse Articles

Nucleophilicity at copper(-I) in a compound with a Cu–Mg bond

Abstract Copper is ubiquitous as a structural material, and as a reagent in (bio)chemical transformations. A vast number of chemical reactions rely on the near-inevitable preference of copper for positive oxidation states to make useful compounds. Here we show this electronic paradigm can be subverted in a stable compound with a copper-magnesium bond, which conforms to the formal oxidation state of Cu(-I). The Cu-Mg bond is synthesized by the reaction of an N-heterocyclic carbene (NHC) ligated copper alkoxide with a dimeric magnesium(I) compound. Its identity is confirmed by single-crystal X-ray structural analysis and NMR spectroscopy, and computational investigations provide data consistent with a high charge density at copper. The Cu-Mg bond acts as a source of the cupride anion, transferring the NHC-copper fragment to electrophilic s-, p-, and d-block atoms to make known and new copper-containing compounds.

Retraction: Preliminary validity of the BNSSS-20 in Arabic: Exploratory study on basic needs satisfaction in sport for a sample of Tunisian athletes

Reply to: On the giant deformation and ferroelectricity of guanidinium nitrate

The role of extra-familial factors in adolescence for the association between out-of-home care and adult psychiatric disorders–A birth cohort study

Background Psychiatric disorders are a substantial public health concern, and childhood adversity a well-known risk factor for it. Investigating gender differences in vulnerability and resilience processes following out-of-home care (OHC) as proxy for childhood adversity can help map opportunities for the prevention of psychiatric disorders. Methods We followed a large birth cohort for psychiatric disorders (anxiety, depression, and self-harm, and substance misuse) between age 25–62 years, comparing individuals with and without OHC experience. We investigated different extra-familial risk and resources factors following OHC via gender-stratified mediation and moderation analyses to approximate risk accumulation (vulnerability processes) and buffers of risk (resilience processes). Results OHC is prospectively associated with psychiatric disorders in adulthood. Lower school grades, delinquency, and early parenthood are mediators of the association, with the exception of education in girls in relation to anxiety, depression, and self-harm, and early parenthood in boys in relation to substance misuse. Number of best friends moderates OHC experience in boys, and there is a trend for higher educational achievement to also act as buffer, even though this trend was not statistically significant. Leisure time activities did not act as buffer. Conclusion Vulnerability and resilience processes after childhood adversity are gendered: Risk accumulation runs via delinquency and poorer educational outcomes in boys more than in girls, while early parenthood is a more dominant risk factor in girls. Having more best friends and higher grades may act as buffer, especially in boys.

Temperature-dependent variations in under-canopy herbaceous foliar diseases following shrub encroachment in grasslands

Toll-like receptor 1/2 activation reduces immunoglobulin free light chain production by multiple myeloma cells in the context of bone marrow stromal cells and fibronectin

Toll-like receptor (TLRs) activation in multiple myeloma (MM) cells induces heterogeneous functional responses including cell growth and proliferation, survival or apoptosis. These effects have been suggested to be partly due to increase in secretion of cytokines such as IL-6 or IFNα among others from MM cells following TLR activation. However, whether triggering of these receptors also modulates production of immunoglobulin free light chains (FLCs), which largely contribute to MM pathology, has not been investigated in MM cells before. This study explored the effect of TLR1/2 ligand (Pam3CSK4) alone or combined with bortezomib (BTZ) on production of FLCs in human myeloma cell lines, L363, OPM-2, U266 and NCI-H929. It also investigated the above effect when MM cells were exposed to bone marrow stromal cells (BMSCs) or fibronectin (FN). Adhesion to BMSCs or FN increased secretion of FLC in MM cells. Pam3CSK4 decreased FLC production, and this effect was enhanced in combination with BTZ but attenuated when MM cells adhered to BMSCs or FN. The findings of this study imply that activation of TLR1/2 downregulates FLC production in MM cells even in the context of bone marrow microenvironment components and suggest that targeting some TLRs such as TLR1/2 might have therapeutic potential.

Ferromagnetic Fe-TiO2 spin catalysts for enhanced ammonia electrosynthesis

Abstract Magnetic field effects (MFE) of ferromagnetic spin electrocatalysts have attracted significant attention due to their potential to enhance catalytic activity under an external magnetic field. However, no ferromagnetic spin catalysts have demonstrated MFE in the electrocatalytic reduction of nitrate for ammonia (NO3RR), a pioneering approach towards NH3 production involving the conversion from diamagnetic NO3 − to paramagnetic NO. Here, we report the ferromagnetic Fe-TiO2 to investigate MFE on NO3RR. Fe-TiO2 possesses a high density of atomically dispersed Fe sites and exhibits an intermediate-spin state, resulting in magnetic ordering through ferromagnetism. Assisted by a magnetic field, Fe-TiO2 achieves a Faradaic efficiency (FE) of up to 97% and an NH3 yield of 24.69 mg mgcat − 1 at −0.5 V versus reversible hydrogen electrode. Compared to conditions without an external magnetic field, the FE and NH3 yield for Fe-TiO2 under an external magnetic field is increased by ~21.8% and ~ 3.1 times, respectively. In-situ characterization and theoretical calculations show that spin polarization enhances the critical step of NO hydrogenation to NOH by optimizing electron transfer pathways between Fe and NO, significantly boosting NO3RR activity.

onEEGwaveLAD: A fully automated online EEG wavelet-based learning adaptive denoiser for artefacts identification and mitigation

Electroencephalographic signals are obtained by amplifying and recording the brain’s spontaneous biological potential using electrodes positioned on the scalp. While proven to help find changes in brain activity with a high temporal resolution, such signals are contaminated by non-stationary and frequent artefacts. A plethora of noise reduction techniques have been developed, achieving remarkable performance. However, they often require multi-channel information and additional reference signals, are not fully automated, require human intervention and are mostly offline. With the popularity of Brain-Computer Interfaces and the application of Electroencephalography in daily activities and other ecological settings, there is an increasing need for robust, online, near real-time denoising techniques, without additional reference signals, that is fully automated and does not require human supervision nor multi-channel information. This research contributes to the body of knowledge by introducing onEEGwaveLAD, a novel, fully automated, ONline, EEG wavelet-based Learning Adaptive Denoiser pipeline for artefact identification and reduction. It is a specific framework that can be instantiated for various types of artefacts paving the path towards real-time denoising. As the first of its kind, it is described and instantiated for the particular problem of blink detection and reduction, and evaluated across a general and a specific analysis of the signal to noise ratio across 30 participants.

Deepening water scarcity in breadbasket nations

Identity as a resource or a demand

Individuals embody various social identities that can impact how they interface with the social environment. Stigma theories suggest that members of low-status or marginalized groups possess devalued social identities, and therefore, experience more stress. While social identities can lead to increased stress, individuals’ appraisals of their identities are not necessarily perceived as harmful/demanding. Rather, social identities can also be appraised as resources or sources of strength bringing opportunities and facilitating goal attainment. Using the biopsychosocial (BPS) model of challenge and threat as a conceptual foundation, this research developed a novel measure to assess individuals’ appraisals of their social identities. In Study 1 (N = 575), confirmatory factor analysis (CFA) evaluated the theorized factor structure (i.e., resource and demand appraisals) and assessed the overall fit of the model. Structural equation modeling (SEM) tested for associations between the resource and demand latent factors. Individuals appraising their ethnic-racial identity as a resource exhibited improved self and intergroup outcomes, while those perceiving it as a demand reported worse self-based and intergroup outcomes, as well as more distress. Study 2 (N = 743 Black and White Americans), which was preregistered, examined group differences in appraisals of ethnic-racial identity. SEM revealed that Black participants were more likely than White participants to appraise their ethnic-racial identity as demanding, leading to worse social and intergroup outcomes. Even when Black participants perceived their ethnic-racial identity as a resource, they still reported higher levels of discrimination, intergroup anxiety, and behavioral avoidance compared to their White counterparts. Implications for theory development and application to the stress literature are discussed.

High-rate quantum LDPC codes for long-range-connected neutral atom registers

Deciphering the dose-dependent effects of thymoquinone on cellular proliferation and transcriptomic changes in A172 glioblastoma cells

Glioblastoma multiforme (GBM), the most prevalent primary malignant brain tumor in adults, exhibits a dismal 6.9% five-year survival rate post-diagnosis. Thymoquinone (TQ), the most abundant bioactive compound in Nigella sativa, has been extensively researched for its anticancer properties across various human cancers. However, its specific anti-cancer mechanisms and pathways in glioblastoma remain to be completely elucidated. In this study, we assessed the impact of different TQ concentrations on the viability of A172 cells using WST-8 and Toluidine blue assays, followed by RNA sequencing (RNA-Seq) to identify differentially expressed genes (DEGs). We confirmed their expression levels through quantitative RT-PCR and performed Gene Ontology and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analyses for these DEGs. RNA-seq revealed no significant gene expression changes at 2.5 μM and 5 μM TQ concentrations. However, at 25 μM and 50 μM, TQ significantly reduced cell viability dose-dependently. We identified 1548 DEGs at 25 μM TQ (684 up-regulated, 864 down-regulated) and 2797 DEGs at 50 μM TQ (1528 up-regulated, 1269 downregulated), with 1202 DEGs common to both concentrations. TQ inhibited key pathways such as PI3K-Akt signaling, calcium signaling, focal adhesion, and ECM-receptor interaction in A172 cells. It downregulated several potential oncogenes (e.g., AEBP1, MIAT) and genes linked to GBM proliferation and migration (e.g., SOCS2, HCP5) while modulating Wnt signaling and up-regulating tumor suppressor genes (e.g., SPRY4, BEX2). TQ also affected p53 downstream targets, maintaining p53 levels. This study elucidates the anti-cancer mechanisms of TQ in A172 GBM cells, underscoring its effects on multiple signaling pathways and positioning TQ as a promising candidate for innovative glioblastoma treatment strategies.

Enhanced phosphorus weathering contributed to Late Miocene cooling

Short-term effects of combined environmental factors on respiratory disease mortality in Qingdao city: A time-series investigation

Background It is crucial to comprehend the interplay between air pollution and meteorological conditions in relation to population health within the framework of "dual-carbon" targets. The purpose of this study was to investigate the impact of intricate environmental factors, encompassing both meteorological conditions and atmospheric pollutants, on respiratory disease (RD) mortality in Qingdao, a representative coastal city in China. Methods The RD mortality cases were collected from the Chronic Disease Surveillance Monitoring System in Qingdao during Jan 1st, 2014 and Dec 31st, 2020. The distributed-lag nonlinear model and generalized additivity model were used to assess the association between daily mean temperature (DMT), air pollutant exposure and RD mortality. To ascertain the robustness of the model and further investigate this relationship, a stratified analysis and sensitivity analysis were conducted to mitigate potential confounding factors. Results A total of 19,905 mortalities from RD were recorded. The minimum mortality temperature (MMT) was determined to be 23.5°C, and DMT and RD mortality showed an N-shaped relationship. At the MMT of 23.5°C, the cumulative relative risk (cumRR) for mortality within a lag period of 0–14 days from the highest temperature (31°C) was estimated at 2.114 (95% confidence interval [CI]: 1.475 ~ 3.028). The effect value of particulate matter (PM) also increased with a longer cumulative lag time. In the single pollutant model, the highest risk of RD mortality was observed on the lag1-day of per 10 μg/m3 increase in PM2.5 exposure, with an excess risk ratio (ER) of 0.847% (95% CI: 0.335% ~ 1.362%). The largest cumulative effect was found at a lag of 8 days, with an ER of 1.546% (95% CI: 0.483% ~ 2.621%). A similar trend was found for PM10. For O3 exposure, the highest risk was observed on the lag1-day of per 10 μg/m3 increase, with an ER of 1.073% (95% CI: 0.502% ~ 1.647%), and the largest cumulative effect occurred at a lag of 2 days with an ER of 1.113% (95%CI: 0.386% ~ 1.844%). Results from the dual-pollutants model demonstrated that the effect of PM on the risk of RD mortality remained significant and slightly increased in magnitude. Moreover, composite pollutants exhibited a higher risk effect, reaching its peak after one week; however, there was a decrease in single-day cumulative effects as more pollutant types were included. Subgroup analysis showed that females, elderly individuals, and those exposed during warm seasons demonstrated greater susceptibility to PM exposure. Conclusion The present study revealed a significant association between short-term exposure to high temperature, PM2.5, PM10 and O3 and the risk of RD mortality in Qingdao, even in dual- and composite-pollutants models. Furthermore, our findings indicate that females, the elderly population, and warm seasons exhibit heightened sensitivity to PM exposure.

Single-cell transcriptomics of bronchoalveolar lavage during PRRSV infection with different virulence

Beauty of symmetry ‐ The impact of logo symmetry on perceived product quality

In an era of intense brand competition, a successful logo can effectively boost consumer awareness of a company. However, existing research has not thoroughly examined the aspect of symmetry in logo design. Addressing this gap, the present study investigates the impact of logo symmetry on consumers’ perceived product quality. Through three online experiments, the results revealed that symmetrical logos significantly enhance perceived product quality compared to asymmetrical logos, with perceived stability mediating this effect. Furthermore, the study confirmed the moderating role of cognitive load, showing that symmetrical logos positively affect perceived product quality only under low cognitive load, while this effect vanishes under high cognitive load. This study contributes to the field of visual logo design and provides practical insights for companies in product promotion and logo design.

Polygenic burden of short tandem repeat expansions promotes risk for Alzheimer’s disease

Comparative efficacy of robot-assisted therapy associated with other different interventions on upper limb rehabilitation after stroke: A protocol for a network meta-analysis

Introduction Post-stroke movement disorders are common, especially upper limb dysfunction, which seriously affects the physical and mental health of stroke patients. With the continuous development of intelligent technology, robot-assisted therapy has become a research hotspot in the upper limb rehabilitation of stroke patients in recent years. Many scholars have also integrated robot-assisted therapy with other interventions to improve rehabilitation outcomes. However, there is a lack of research to determine which auxiliary intervention is the best. Therefore, this protocol aims to guide the development of a network meta-analysis, which helps determine the most suitable auxiliary interventions for robot-assisted therapy. Methods and analysis Published randomized controlled trials will be included if robot-assisted therapy or robot-assisted therapy associated with other different interventions was applied in stroke patients with upper limb dysfunction in the experimental group and usual rehabilitation treatment and care was applied in the control group. CINAHL, PubMed, Web of Science, MEDLINE, Embase, CNKI, and Wanfang electronic databases will be searched. Studies should be published between January 1, 2013, and December 31, 2023. Two reviewers will independently select studies and extra data, and assess the quality of the included studies. The risk of bias will be evaluated based on the Cochrane Collaboration’s risk of bias tool. The evidence quality will be measured according to the Grading of Recommendations Assessment, Development and Evaluation. A network meta-analysis will be conducted by using STATA version 15.0 and R version 4.1.3. The probabilities of rehabilitation interventions will be ranked according to the surface under the cumulative ranking curve. Ethics and dissemination Ethical approval is not needed for reviewing published studies. The results will be submitted to a journal. Trial registration PROSPERO registration number: CRD42023486570.

Anisotropic hydrogel microelectrodes for intraspinal neural recordings in vivo

Racial disparities in extended venous thromboembolism prophylaxis after hysterectomy

Background Venous thromboembolism (VTE) is a significant preventable cause of postoperative morbidity and mortality after major abdominopelvic surgery that calls for extended VTE prophylaxis (eVTEp). Literature suggests that significant racial disparities may exist in post-operative care. Objective The study sought to examine if racial disparities exist in the administration of eVTEp after hysterectomy in a statewide collaborative. Methods We conducted a retrospective cohort study of post-hysterectomy patients across 69 hospitals in the Michigan Surgical Quality Collaborative from January 2016 to February 2020. The variable of interest was race (Black/African or White American). The primary outcome was administration or absence of eVTEp. Descriptive statistics and mixed effects logistic regression were performed for risk adjustment with covariates such as age, cancer occurrence, inflammatory bowel disease, American Society of Anesthesiologists physical status classification, perioperative VTE prophylaxis, postoperative VTE prophylaxis, surgical approach, and surgical duration, among other variables. Results In total, 24,513 patients underwent hysterectomy. Of these patients, 1,107 (4.45%) received eVTEp, 153 (13.24%) of which were Black and 954 (82.53%) of which were White. Mixed effects logistic regression analysis suggested that Black patients were significantly less likely to receive eVTEp than White patients (odds ratio = 0.776; 95% CI: 0.615–0.979; P = 0.039). Additionally, tobacco use, coronary artery disease, bleeding disorder, cancer occurrence, functional status, perioperative VTE prophylaxis, surgical duration, length of stay, and surgical approach were associated with a higher likelihood of receiving eVTEp. Conclusion eVTEp is recommended for the prevention of post-discharge VTE in select patients after hysterectomy. Regression analysis showed that, compared to their White counterparts, Black females were significantly less likely to receive eVTEp. The underlying reasons for this disparity require further investigation into possible socioeconomic influences and inherent biases.