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This study characterized the effect of calorie restriction (CR) on elemental content and stable isotope ratio measurements of bone "collagen" and hair keratin. Adult mice on graded CR (10-40%; 84 days) showed decreased hair δ 15N, δ 13C, and δ 34S values (significantly for δ 15N) with increasing CR, alongside a significant increase in bone "collagen" δ 15N values and a decrease in "collagen" δ 13C values. We propose this was likely due to the intensified mobilization of endogenous proteins, as well as lipids in newly synthesized "collagen". Elemental analysis of bone "collagen" revealed decreased carbon, nitrogen, and sulfur % content with increasing CR which is attributed to a change in the in vivo bone "collagen" structure with extent of CR. This complexity challenges the use of elemental indicators in the assessment of collagen quality in archaeological studies where nutritional stress may be a factor.
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Curious about how chemistry can contribute to sustainable development? In this overview, we explain the essence of NCCR funding, the research focus and structural goals of NCCR Catalysis, and how these align with the sustainable development goals (SDGs). Additionally, we highlight opportunities for getting involved with our program.
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Caloric restriction (CR) results in reduced energy and protein intake, raising questions about protein restriction's contribution to CR longevity benefits. We kept ad libitum (AL)-fed male C57BL/6J mice at 27°C (AL27) and pair-fed (PF) mice at 22°C (22(PF27)). The 22(PF27) group was fed to match AL27 while restricted for calories due to cold-induced metabolism. The 22(PF27) mice had significantly lower body weight, lean mass, fat mass, leptin, IGF-1, and TNF-α levels than AL27 mice (p<0.001 for all). Manipulations over ~11 weeks resulted in significant differences in body temperature, physical activity, and expression of key genes linked to hunger in the hypothalamus. Survival was significantly greater in 22(PF27) compared to AL27 overall (p<0.001). CR in the context of equivalent energy and protein intake resulted in hormonal, metabolic, and physiological benefits and extended longevity. Hence, energy imbalance, rather than low energy or protein intake per se, mediates the benefits of CR.
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Dietary protein modulates food intake (FI) via unclear mechanism(s). One possibility is that higher protein leads to greater post-ingestive heat production (Specific dynamic action: SDA) leading to earlier meal termination (increased satiation), and inhibition of further intake (increased satiety). The influence of dietary protein on feeding behaviour in C57BL/6J mice was tested using an automated FI monitoring system (BioDAQ), simultaneous to body temperature (Tb). Total FI, inter meal intervals (IMI, satiety) and meal size (MS, satiation) were related to changes in Tb after consuming low (5%, LP), moderate (15%, MP) and high (30%, HP) protein diets. Diets were tested over three conditions: 1) room temperature (RT, 21 ± 1 °C), 2) room temperature and running wheels (RTRW) and 3) low temperature (10 °C) and running wheels (LTRW). The differences between diets and conditions were also compared using mixed models. Mice housed at RT fed HP diet, reduced total FI compared with LP and MP due to earlier meal termination (satiation effect). FI was lowered in RTRW conditions with no differences between diets. FI significantly increased under LTRW conditions for all diets, with protein content leading to earlier meal termination (satiation) but not the intervals between feeding bouts (satiety). Tb fell immediately after feeding in all conditions. Despite a reduction in total FI in mice fed HP, mediated via increased satiation, this effect was not linked to increased Tb during meals. We conclude effects of dietary protein on intake are not mediated via SDA and Tb.
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Temperatura Corporal , Proteínas Alimentares , Camundongos Endogâmicos C57BL , Saciação , Animais , Proteínas Alimentares/administração & dosagem , Proteínas Alimentares/farmacologia , Masculino , Camundongos , Comportamento Alimentar/fisiologia , Ingestão de Alimentos/fisiologia , Resposta de SaciedadeRESUMO
Chemistry, a vital tool for sustainable development, faces a challenge due to the lack of clear guidance on actionable steps, hindering the optimal adoption of sustainability practices across its diverse facets from discovery to implementation. This Scientific Perspective explores established frameworks and principles, proposing a conciliated set of tripleâ E priorities anchored on Environmental, Economic, and Equity pillars for research and decision making. We outline associated metrics, crucial for quantifying impacts, classifying them according to their focus areas and scales tackled. Emphasizing catalysis as a key driver of sustainable synthesis of chemicals and materials, we exemplify how tripleâ E priorities can practically guide the development and implementation of processes from renewables conversions to complex customized products. We summarize by proposing a roadmap for the community aimed at raising awareness, fostering academia-industry collaboration, and stimulating further advances in sustainable chemical technologies across their broad scope.
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Climate change poses a significant threat to food security and global public health with the increasing likelihood of insect pest outbreaks. Alternative ways to control insect populations, preferably using environmental-friendly compounds, are needed. Turmeric has been suggested as a natural insecticide with toxicity properties in some insect groups. However, empirical evidence of the effects of turmeric - and their interaction with other ecological factors such as diet - on insect survival has been limited. Here, we tested the effects of turmeric and its interactions with diets differing in protein source in the common housefly, Musca domestica. We found that turmeric shortened lifespan independent of diet and sex. Females in turmeric diets were heavier at death, which was likely driven by a combination of relatively lower rates of body mass loss during their lifetime and a higher percentage of water content at death. Each sex responded differently to the protein source in the diet, and the magnitude of the difference in lifespan between sexes were greatest in diets in which protein source was hydrolysed yeast; individuals from both sexes lived longest in sucrose-milk diets and shortest in diets with hydrolysed yeast. There was no evidence of an interaction between turmeric and diet, suggesting that the toxicity effects are independent of protein source in the diet. Given the seemingly opposing effects of turmeric in insects and mammals being uncovered in the literature, our findings provide further evidence in support of turmeric as a potential natural insecticide.
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Metal promotion could unlock high performance in zinc-zirconium catalysts, ZnZrOx, for CO2 hydrogenation to methanol. Still, with most efforts devoted to costly palladium, the optimal metal choice and necessary atomic-level architecture remain unclear. Herein, we investigate the promotion of ZnZrOx catalysts with small amounts (0.5 mol%) of diverse hydrogenation metals (Re, Co, Au, Ni, Rh, Ag, Ir, Ru, Pt, Pd, and Cu) prepared via a standardized flame spray pyrolysis approach. Cu emerges as the most effective promoter, doubling methanol productivity. Operando X-ray absorption, infrared, and electron paramagnetic resonance spectroscopic analyses and density functional theory simulations reveal that Cu0 species form Zn-rich low-nuclearity CuZn clusters on the ZrO2 surface during reaction, which correlates with the generation of oxygen vacancies in their vicinity. Mechanistic studies demonstrate that this catalytic ensemble promotes the rapid hydrogenation of intermediate formate into methanol while effectively suppressing CO production, showcasing the potential of low-nuclearity metal ensembles in CO2-based methanol synthesis.
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BACKGROUND: During the pandemic, all universities had to switch to digital learning and teaching (DLT), the experiences were diverse. The advantages and obstacles of DLT are well reported in research. To ensure a sustainable DLT implementation, the requirements of institutions, educators and students should be aligned. OBJECTIVE: This paper aims at identifying and describing the experiences made at the Swiss medical schools after having to switch from on-site to on-line teaching; in particular, the experienced issues, requirements, and solutions were investigated and compared to international literature. METHODS: We conducted a literature review to derive themes and subthemes regarding the central aspects of the transition from on-site to on-line teaching. Also, we conducted semi-structured interviews with people responsible for the medical curricula at the Swiss Medical Schools. We used a purposive sampling method and invited eleven curriculum managers at the seven Swiss Medical Schools. The interviews were conducted in English, audio-recorded and transcribed. Subsequently the data was analysed with the software NVivo. We used a qualitative, deductive, content analysis to explore faculty experiences. RESULTS: Twenty-four articles met the eligibility criteria and were included for full text screening. Of the included articles, 15 reported on DLT in general and nine articles reported on DLT during the Pandemic. The thematic analysis of the interviews resulted in four overall themes, requirements, obstacles, facilitators and advantages. Curriculum managers reported that institutions were relatively unprepared for the quick transition from onsite to online at the onset of the pandemic. CONCLUSIONS: Our research reports a lack of institutional structures, communication, digital competences and literacy, teaching strategies, as well as a theoretical foundation for DLT implementation. A conceptual framework for DLT adapted to the Swiss universities beyond the current situation is needed.
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COVID-19 , Pandemias , Humanos , Faculdades de Medicina , Suíça , COVID-19/epidemiologia , AprendizagemRESUMO
Single-atom heterogeneous catalysts (SACs) hold promise as sustainable alternatives to metal complexes in organic transformations. However, their working structure and dynamics remain poorly understood, hindering advances in their design. Exploiting the unique features of droplet-based microfluidics, we present the first in-situ assessment of a palladium SAC based on exfoliated carbon nitride in Suzuki-Miyaura cross-coupling using X-ray absorption spectroscopy. Our results confirm a surface-catalyzed mechanism, revealing the distinct electronic structure of active Pd centers compared to homogeneous systems, and providing insights into the stabilizing role of ligands and bases. This study establishes a valuable framework for advancing mechanistic understanding of organic syntheses catalyzed by SACs.
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C1 coupling reactions over zeolite catalysts are central to sustainable chemical production strategies. However, questions persist regarding the involvement of CO in ketene formation, and the impact of this elusive oxygenate intermediate on reactivity patterns. Using operando photoelectron photoion coincidence spectroscopy (PEPICO), we investigate the role of CO in methyl chloride conversion to hydrocarbons (MCTH), a prospective process for methane valorization with a reaction network akin to methanol to hydrocarbons (MTH) but without oxygenate intermediates. Our findings reveal the transformative role of CO in MCTH at the low pressures, inducing ketene formation in MCTH and boosting olefin production, confirming the Koch carbonylation step in the initial stages of C1 coupling. We uncover pressure-dependent product distributions driven by CO-induced ketene formation, and its subsequent desorption from the zeolite surface, which is enhanced at low pressure. Inspired by the above results, extension of the co-feeding approach to CH3OH as another simple oxygenate showcases the additional potential for improved catalyst stability in MCTH at ambient pressure.
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INTRODUCTION: Applying the lens of social constructivist theory, teaching methods facilitate the process of learning and may be used differently across settings to align learning goals. Teaching methods are used across disciplines, occupations and learning settings, yet terminology, descriptions and application for use vary widely. This scoping review will identify eligible literature of reported teaching methods with documented descriptions across disciplines with a focus of how teaching methods are applied to health professions education. A literary description of a teaching method was used as a basis from which to select eligible articles based on two criteria, a specified method and delivery of that teaching by a teacher figure. METHODS AND ANALYSIS: Using the extension of the Joanna Briggs Institute methodology aligned to Arksey and O'Malley's six-stage framework and the Preferred Reporting Items for Systematic Reviews and Meta-Analyses extension for Scoping Reviews guidelines, this scoping review will systematically search ERIC, Embase, Web of Science and PubMed databases. The search strategy was supported by an information specialist. Eligible studies will be identified in a two-stage screening process with four researchers. To complement eligible peer-reviewed literature, we will also search out relevant grey literature including University Websites, Conference Programmes and handsearched reference lists. Data extraction will be performed using a developed data extraction tool. A narrative summary will accompany charted results and describe the results aligned to the study objectives. ETHICS AND DISSEMINATION: As no intervention or patient recruitment is required for this research, ethics board approval is not required. Results will be disseminated via publication in a peer-reviewed journal, conference presentations and where feasible reaching out to those organisations and universities with published glossaries of terms for teaching.
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Ocupações em Saúde , Ensino , Humanos , Ocupações em Saúde/educação , Revisão por Pares , Revisões Sistemáticas como AssuntoRESUMO
Ultra-high-density single-atom catalysts (UHD-SACs) present unique opportunities for harnessing cooperative effects between neighboring metal centers. However, the lack of tools to establish correlations between the density, types, and arrangements of isolated metal atoms and the support surface properties hinders efforts to engineer advanced material architectures. Here, this work precisely describes the metal center organization in various mono- and multimetallic UHD-SACs based on nitrogen-doped carbon (NC) supports by coupling transmission electron microscopy with tailored machine-learning methods (released as a user-friendly web app) and density functional theory simulations. This approach quantifies the non-negligible presence of multimers with increasing atom density, characterizes the size and shape of these low-nuclearity clusters, and identifies surface atom density criteria to ensure isolation. Further, it provides previously inaccessible experimental insights into coordination site arrangements in the NC host, uncovering a repulsive interaction that influences the disordered distribution of metal centers in UHD-SACs. This observation holds in multimetallic systems, where chemically-specific analysis quantifies the degree of intermixing. These fundamental insights into the materials chemistry of single-atom catalysts are crucial for designing catalytic systems with superior reactivity.
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Synthesis protocol exploration is paramount in catalyst discovery, yet keeping pace with rapid literature advances is increasingly time intensive. Automated synthesis protocol analysis is attractive for swiftly identifying opportunities and informing predictive models, however such applications in heterogeneous catalysis remain limited. In this proof-of-concept, we introduce a transformer model for this task, exemplified using single-atom heterogeneous catalysts (SACs), a rapidly expanding catalyst family. Our model adeptly converts SAC protocols into action sequences, and we use this output to facilitate statistical inference of their synthesis trends and applications, potentially expediting literature review and analysis. We demonstrate the model's adaptability across distinct heterogeneous catalyst families, underscoring its versatility. Finally, our study highlights a critical issue: the lack of standardization in reporting protocols hampers machine-reading capabilities. Embracing digital advances in catalysis demands a shift in data reporting norms, and to this end, we offer guidelines for writing protocols, significantly improving machine-readability. We release our model as an open-source web application, inviting a fresh approach to accelerate heterogeneous catalysis synthesis planning.
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Scaling up syntheses from mg to kg quantities is a complex endeavor. Besides adapting laboratory protocols to industrial processes and equipment and thorough safety assessments, much attention is paid to the reduction of the process' environmental impact. For processes including transition metal catalyzed steps, e.g. cross-coupling chemistry, this impact strongly depends on the identity of the metal used. As such, a key approach is the replacement of single-use with reusable heterogeneous catalysts. Transition metal single-atom heterogeneous catalysts (SAC), a novel class of catalytic materials, might exhibit all the necessary properties to step up to this task. This article shall discuss current applications of SAC in cross-coupling chemistry from the point of a process chemist and shed light on the NCCR Catalysis contribution to the field. Investigations of the stability-activity-selectivity relationship of SACs in combination with early-stage life-cycle assessments (LCA) of potential processes lay the foundation for large-scale application tailored catalyst synthesis. Ultimately, prevailing challenges are highlighted, which need to be addressed in future research.
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Single-atom heterogeneous catalysts (SACs) attract growing interest in their application in green chemistry and organic synthesis due to their potential for achieving atomic-level precision. These catalysts offer the possibility of achieving selectivity comparable to the traditionally applied organometallic complexes, while enhancing metal utilization and recovery. However, an understanding of SAC performance in organic reactions remains limited to model substrates, and their application as drop-in solutions may not yield optimal activity. Here, we investigate the previously unaddressed influence of the reaction environment, including solvent, base, cocatalyst, and ligand, on the performance of a palladium SAC in Sonogashira-Hagihara cross-couplings. By examining the effects of different solvents using the established criteria, we find that the behavior of the SAC deviates from trends observed with homogeneous catalysts, indicating a distinct interplay between heterogeneous systems and the reaction environment. Our results illustrate the satisfactory performance of SACs in cross-couplings of aryl iodides and acetylenes with electron-withdrawing and -donating groups, while the use of bromides and chlorides remains challenging. Extending the proof-of-concept stage to multigram scale, we demonstrate the synthesis of an intermediate of the anticancer drug Erlotinib. The catalyst exhibits high stability, allowing for multiple reuses, even under noninert conditions. Life-cycle assessment guides the upscaling of the catalyst preparation and quantifies the potential environmental and financial benefits of using the SAC, while also revealing the negligible impact of the PPh3 ligand and CuI cocatalyst. Our results underscore the significant potential of SACs to revolutionize sustainable organic chemistry and highlight the need for further understanding the distinct interplay between their performance and the reaction environment.
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Heterogeneous single-cluster catalysts (SCCs) comprising atomically precise and isolated metal clusters stabilized on appropriately chosen supports offer exciting prospects for enabling novel chemical reactions owing to their broad structural diversity with unparalled opportunities for engineering their properties. Although the pioneering work revealed intriguing performance trends of size-selected metal clusters deposited on supports, synthetic and analytical challenges hindered a thorough understanding of surface chemistry under realistic conditions. This Review underscores the importance of considering the cluster environment in SCCs, encompassing the development of robust metal-support interactions, precise control over the ligand sphere, the influence of reaction media and dynamic behaviour, to uncover new reactivities. Through examples, we illustrate the criticality of tailoring the entire catalytic ensemble in SCCs to achieve stable and selective performance with practically relevant metal coverages. This expansion in application scope transcends from model reactions to complex and technically relevant reactions. Furthermore, we provide a perspective on the opportunities and future directions for SCC design within this rapidly evolving field.
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Single-atom catalysts (SACs) have well-defined active sites, making them of potential interest for organic synthesis1-4. However, the architecture of these mononuclear metal species stabilized on solid supports may not be optimal for catalysing complex molecular transformations owing to restricted spatial environment and electronic quantum states5,6. Here we report a class of heterogeneous geminal-atom catalysts (GACs), which pair single-atom sites in specific coordination and spatial proximity. Regularly separated nitrogen anchoring groups with delocalized π-bonding nature in a polymeric carbon nitride (PCN) host7 permit the coordination of Cu geminal sites with a ground-state separation of about 4 Å at high metal density8. The adaptable coordination of individual Cu sites in GACs enables a cooperative bridge-coupling pathway through dynamic Cu-Cu bonding for diverse C-X (X = C, N, O, S) cross-couplings with a low activation barrier. In situ characterization and quantum-theoretical studies show that such a dynamic process for cross-coupling is triggered by the adsorption of two different reactants at geminal metal sites, rendering homo-coupling unfeasible. These intrinsic advantages of GACs enable the assembly of heterocycles with several coordination sites, sterically congested scaffolds and pharmaceuticals with highly specific and stable activity. Scale-up experiments and translation to continuous flow suggest broad applicability for the manufacturing of fine chemicals.
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Understanding aging is a key biological goal. Precision gerontology aims to predict how long individuals will live under different treatment scenarios. Calorie and protein restriction (CR and PR) extend lifespan in many species. Using data from C57BL/6 male mice under graded CR or PR, we introduce a computational thermodynamic model for entropy generation, which predicted the impact of the manipulations on lifespan. Daily entropy generation decreased significantly with increasing CR level, but not PR. Our predictions indicated the lifespan of CR mice should increase by 13 to 56% with 10 to 40% CR, relative to ad libitum-fed animals. This prediction was broadly consistent with the empirical observation of the lifespan impacts of CR in rodents. Modeling entropy fluxes may be a future strategy to identify antiaging interventions.
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Geriatria , Longevidade , Masculino , Animais , Camundongos , Camundongos Endogâmicos C57BL , Entropia , Dieta com Restrição de ProteínasRESUMO
Ternary Pd-In2 O3 /ZrO2 catalysts exhibit technological potential for CO2 -based methanol synthesis, but developing scalable systems and comprehending complex dynamic behaviors of the active phase, promoter, and carrier are key for achieving high productivity. Here, we show that the structure of Pd-In2 O3 /ZrO2 systems prepared by wet impregnation evolves under CO2 hydrogenation conditions into a selective and stable architecture, independent of the order of addition of Pd and In phases on the zirconia carrier. Detailed operando characterization and simulations reveal a rapid restructuring driven by the metal-metal oxide interaction energetics. The proximity of InPdx alloy particles decorated by InOx layers in the resulting architecture prevents performance losses associated with Pd sintering. The findings highlight the crucial role of reaction-induced restructuring in complex CO2 hydrogenation catalysts and offer insights into the optimal integration of acid-base and redox functions for practical implementation.