MAATrica: a measure for assessing consistency and methods in medicinal and nutraceutical chemistry papers.

The growing number of scientific papers and document sources underscores the need for methods capable of evaluating the quality of publications. Researchers who are looking for relevant papers for their studies need ways to assess the scientific value of these documents. One approach involves using semantic search engines that can automatically extract important knowledge from the growing body of text. In this study, we introduce a new metric called "MAATrica," which serves as the foundation for an innovative method designed to evaluate research papers. MAATrica offers a new way to analyze and categorize text, focusing on the consistency of research documents in the life sciences, particularly in the fields of medicinal and nutraceutical chemistry. This method utilizes semantic descriptions to cover in silico experiments, as well as in vitro and in vivo essays. Created to aid in evaluation processes like peer review, MAATrica uses toolkits and semantic applications to build the proposed measure, identify scientific entities, and gather information. We have applied MAATrica to roughly 90,000 papers and present our findings here.

A Ce-CuZn catalyst with abundant Cu/Zn-OV-Ce active sites for CO2 hydrogenation to methanol.

CO2 hydrogenation to chemicals and fuels is a significant approach for achieving carbon neutrality. It is essential to rationally design the chemical structure and catalytic active sites towards the development of efficient catalysts. Here we show a Ce-CuZn catalyst with enriched Cu/Zn-OV-Ce active sites fabricated through the atomic-level substitution of Cu and Zn into Ce-MOF precursor. The Ce-CuZn catalyst exhibits a high methanol selectivity of 71.1% and a space-time yield of methanol up to 400.3 g·kgcat-1·h-1 with excellent stability for 170 h at 260 °C, comparable to that of the state-of-the-art CuZnAl catalysts. Controlled experiments and DFT calculations confirm that the incorporation of Cu and Zn into CeO2 with abundant oxygen vacancies can facilitate H2 dissociation energetically and thus improve CO2 hydrogenation over the Ce-CuZn catalyst via formate intermediates. This work offers an atomic-level design strategy for constructing efficient multi-metal catalysts for methanol synthesis through precise control of active sites.

Study of repertoire use reveals unexpected context-dependent vocalizations in bottlenose dolphins (Tursiops truncatus).

Dolphins are known for their complex vocal communication, not least because of their capacity for acoustic plasticity. Paradoxically, we know little about their capacity for flexible vocal use. The difficulty in describing the behaviours performed underwater while vocalizing makes it difficult to analyse the contexts of emissions. Dolphins' main vocal categories are typically considered to be used for scanning the environment (clicks), agonistic encounters (burst pulses) and socio-affiliative interactions (whistles). Dolphins can also combine these categories in mixed vocal emissions, whose use remains unclear. To better understand how vocalizations are used, we simultaneously recorded vocal production and the associated behaviours by conducting underwater observations (N = 479 events) on a group of 7 bottlenose dolphins under human care. Our results showed a non-random association between vocal categories and behavioural contexts. Precisely, clicks were preferentially emitted during affiliative interactions and not during other social/solitary contexts, supporting a possible complementary communicative function. Burst pulses were associated to high arousal contexts (agonistic and social play), pinpointing on their use as an "emotively charged" signal. Whistles were related to solitary swimming and not preferentially produced in any social context. This questions whistles' functions and supports their potential role as a distant contact call. Finally, mixed vocalizations were especially found associated with sexual (bust pulse-whistle-click), solitary play (burst pulse-whistle) and affiliative (click-whistle) behaviours. Depending on the case, their emission seems to confirm, modify or refine the functions of their simple counterparts. These results open up new avenues of research into the contextual use of dolphin acoustic signals.

Development of a versatile electrochemical cell for in situ grazing-incidence X-ray diffraction during non-aqueous electrochemical nitrogen reduction.

In situ techniques are essential to understanding the behavior of electrocatalysts under operating conditions. When employed, in situ synchrotron grazing-incidence X-ray diffraction (GI-XRD) can provide time-resolved structural information of materials formed at the electrode surface. In situ cells, however, often require epoxy resins to secure electrodes, do not enable electrolyte flow, or exhibit limited chemical compatibility, hindering the study of non-aqueous electrochemical systems. Here, a versatile electrochemical cell for air-free in situ synchrotron GI-XRD during non-aqueous Li-mediated electrochemical N2 reduction (Li-N2R) has been designed. This cell not only fulfills the stringent material requirements necessary to study this system but is also readily extendable to other electrochemical systems. Under conditions relevant to non-aqueous Li-N2R, the formation of Li metal, LiOH and Li2O as well as a peak consistent with the α-phase of Li3N was observed, thus demonstrating the functionality of this cell toward developing a mechanistic understanding of complicated electrochemical systems.

Ferricyanide photo-aquation pathway revealed by combined femtosecond Kß main line and valence-to-core x-ray emission spectroscopy.

Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kß main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kß main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.

Understanding the Stability of Manganese Chromium Antimonate Electrocatalysts through Multimodal In Situ and Operando Measurements.

Improving electrocatalyst stability is critical for the development of electrocatalytic devices. Herein, we utilize an on-line electrochemical flow cell coupled with an inductively coupled plasma-mass spectrometer (ICP-MS) to characterize the impact of composition and reactant gas on the multielement dissolution of Mn(-Cr)-Sb-O electrocatalysts. Compared to Mn2O3 and Cr2O3 oxides, the antimonate framework stabilizes Mn at OER potentials and Cr at both ORR and OER potentials. Furthermore, dissolution of Mn and Cr from Mn(-Cr) -Sb-O is driven by the ORR reaction rate, with minimal dissolution under N2. We observe preferential dissolution of Cr totaling 13% over 10 min at 0.3, 0.6, and 0.9 V vs RHE, with only 1.5% loss of Mn, indicating an enrichment of Mn at the surface of the particles. Despite this asymmetric dissolution, operando X-ray absorption spectroscopy (XAS) showed no measurable changes in the Mn K-edge at comparable potentials. This could suggest that modification to the Mn oxidation state and/or phase in the surface layer is too small or that the layer is too thin to be measured with the bulk XAS measurement. Lastly, on-line ICP-MS was used to assess the effects of applied potential, scan rate, and current on Mn-Cr-Sb-O during cyclic voltammetry and accelerated stress tests. With this deeper understanding of the interplay between oxygen reduction and dissolution, testing procedures were identified to maximize both activity and stability. This work highlights the use of multimodal in situ characterization techniques in tandem to build a more complete model of stability and develop protocols for optimizing catalyst performance.

Investigation of the Structure of Atomically Dispersed NiNx Sites in Ni and N-Doped Carbon Electrocatalysts by 61Ni Mössbauer Spectroscopy and Simulations.

Ni and nitrogen-doped carbons are selective catalysts for CO2 reduction to CO (CO2R), but the hypothesized NiNx active sites are challenging to probe with traditional characterization methods. Here, we synthesize 61Ni-enriched model catalysts, termed 61NiPACN, in order to apply 61Ni Mössbauer spectroscopy using synchrotron radiation (61Ni-SR-MS) to characterize the structure of these atomically dispersed NiNx sites. First, we demonstrate that the CO2R results and standard characterization techniques (SEM, PXRD, XPS, XANES, EXAFS) point to the existence of dispersed Ni active sites. Then, 61Ni-SR-MS reveal significant internal magnetic fields of ∼5.4 T, which is characteristic of paramagnetic, high-spin Ni2+, in the 61NiPACN samples. Finally, theoretical calculations for a variety of Ni-Nx moieties confirm that high-spin Ni2+ is stable in non-planar, tetrahedrally distorted geometries, which results in calculated isotropic hyperfine coupling that is consistent with 61Ni-SR-MS measurements.

A Behavioral Approach to the Tourism Consumer Decisions of Generation Z.

The main objective of our research is to identify the impact of recycling and waste reduction behavior on the sustainable tourism decisions of Romanian youngsters (18-25 years old). We used the PLS-SEM method and introduced four variables in the model: sustainable tourism decisions, the interest in recycling, the interest in waste reduction, and the interest in natural and less polluted touristic destinations. The main results emphasize the direct influence of recycling and waste reduction behaviors on the decisions made by Generation Z regarding sustainable tourism and on their preference for destinations that are better preserved and less touched by human intervention. The novelty of our research consists of the fact that we introduced variables such as waste reduction from the perspective of tourists because most studies address it as a management approach of the companies in the tourism sector. The findings are useful for managers in the tourism sector to create better strategies for attracting the younger generation who are preoccupied by environmental issues and sustainability in general.

Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS2.

The nature of the S-vacancy is central to controlling the electronic properties of monolayer MoS2. Understanding the geometric and electronic structures of the S-vacancy on the basal plane of monolayer MoS2 remains elusive. Here, operando S K-edge X-ray absorption spectroscopy shows the formation of clustered S-vacancies on the basal plane of monolayer MoS2 under reaction conditions (H2 atmosphere, 100-600 °C). First-principles calculations predict spectral fingerprints consistent with the experimental results. The Mo K-edge extended X-ray absorption fine structure shows the local structure as coordinatively unsaturated Mo with 4.1 ± 0.4 S atoms as nearest neighbors (above 400 °C in an H2 atmosphere). Conversely, the 6-fold Mo-Mo coordination in the crystal remains unchanged. Electrochemistry confirms similar active sites for hydrogen evolution. The identity of the S-vacancy defect on the basal plane of monolayer MoS2 is herein elucidated for applications in optoelectronics and catalysis.

First-Row Transition Metal Antimonates for the Oxygen Reduction Reaction.

The development of inexpensive and abundant catalysts with high activity, selectivity, and stability for the oxygen reduction reaction (ORR) is imperative for the widespread implementation of fuel cell devices. Herein, we present a combined theoretical-experimental approach to discover and design first-row transition metal antimonates as excellent electrocatalytic materials for the ORR. Theoretically, we identify first-row transition metal antimonates─MSb2O6, where M = Mn, Fe, Co, and Ni─as nonprecious metal catalysts with good oxygen binding energetics, conductivity, thermodynamic phase stability, and aqueous stability. Among the considered antimonates, MnSb2O6 shows the highest theoretical ORR activity based on the 4e- ORR kinetic volcano. Experimentally, nanoparticulate transition metal antimonate catalysts are found to have a minimum of a 2.5-fold enhancement in intrinsic mass activity (on transition metal mass basis) relative to the corresponding transition metal oxide at 0.7 V vs RHE in 0.1 M KOH. MnSb2O6 is the most active catalyst under these conditions, with a 3.5-fold enhancement on a per Mn mass activity basis and 25-fold enhancement on a surface area basis over its antimony-free counterpart. Electrocatalytic and material stability are demonstrated over a 5 h chronopotentiometry experiment in the stability window identified by theoretical Pourbaix analysis. This study further highlights the stable and electrically conductive antimonate structure as a framework to tune the activity and selectivity of nonprecious metal oxide active sites for ORR catalysis.

Melanoma-derived extracellular vesicles mediate lymphatic remodelling and impair tumour immunity in draining lymph nodes.

Tumour-draining lymph nodes (LNs) undergo massive remodelling including expansion of the lymphatic sinuses, a process that has been linked to lymphatic metastasis by creation of a pre-metastatic niche. However, the signals leading to these changes have not been completely understood. Here, we found that extracellular vesicles (EVs) derived from melanoma cells are rapidly transported by lymphatic vessels to draining LNs, where they selectively interact with lymphatic endothelial cells (LECs) as well as medullary sinus macrophages. Interestingly, uptake of melanoma EVs by LN-resident LECs was partly dependent on lymphatic VCAM-1 expression, and induced transcriptional changes as well as proliferation of those cells. Furthermore, melanoma EVs shuttled tumour antigens to LN LECs for cross-presentation on MHC-I, resulting in apoptosis induction in antigen-specific CD8+ T cells. In conclusion, our data identify EV-mediated melanoma-LN LEC communication as a new pathway involved in tumour progression and tumour immune inhibition, suggesting that EV uptake or effector mechanisms in LECs might represent a new target for melanoma therapy.

First evidence of yawn contagion in a wild monkey species.

Yawn contagion occurs when individuals yawn in response to the yawn of others (triggers). This is the first account of yawn contagion in wild geladas (Theropithecus gelada), a monkey species that shows yawn contagion in captivity and is organized in core units (one-male/bachelor groups) forming multilevel associations. In a population of geladas from the Kundi plateau (Ethiopia) we found that the yawning response was highest when geladas could perceive a triggering yawn, which confirms that yawn contagion is present in the wild. Yawn duration, mouth-opening degree and presence/absence of vocalisation (possibly modulating yawn detectability) did not affect the likelihood of contagion. Males and females, known to be both implicated in movement initiation within groups, were similarly powerful as yawn triggers. Instead, group membership and responder sex had a significant role in shaping the phenomenon. Yawn contagion was highest between individuals belonging to different core units and males were most likely to respond to others' yawns. Because males have a non-negligible role in inter-group coordination, our results suggest that yawn contagion may have a communicative function that goes beyond the basic unit level.

Origin of enhanced water oxidation activity in an iridium single atom anchored on NiFe oxyhydroxide catalyst.

The efficiency of the synthesis of renewable fuels and feedstocks from electrical sources is limited, at present, by the sluggish water oxidation reaction. Single-atom catalysts (SACs) with a controllable coordination environment and exceptional atom utilization efficiency open new paradigms toward designing high-performance water oxidation catalysts. Here, using operando X-ray absorption spectroscopy measurements with calculations of spectra and electrochemical activity, we demonstrate that the origin of water oxidation activity of IrNiFe SACs is the presence of highly oxidized Ir single atom (Ir5.3+) in the NiFe oxyhydroxide under operating conditions. We show that the optimal water oxidation catalyst could be achieved by systematically increasing the oxidation state and modulating the coordination environment of the Ir active sites anchored atop the NiFe oxyhydroxide layers. Based on the proposed mechanism, we have successfully anchored Ir single-atom sites on NiFe oxyhydroxides (Ir0.1/Ni9Fe SAC) via a unique in situ cryogenic-photochemical reduction method that delivers an overpotential of 183 mV at 10 mA ⋅ cm-2 and retains its performance following 100 h of operation in 1 M KOH electrolyte, outperforming the reported catalysts and the commercial IrO2 catalysts. These findings open the avenue toward an atomic-level understanding of the oxygen evolution of catalytic centers under in operando conditions.

Wild geladas (Theropithecus gelada) in crops-more than in pasture areas-reduce aggression and affiliation.

Human-primate interfaces are expanding and, despite recent studies on primates from peri-urban environments, little research exists on the impact of agriculture and/or pasture areas on primate social behavior and health. We assessed how crop/pasture areas potentially alter social behavior and health of wild geladas (Theropithecus gelada) frequenting the unprotected area of Kundi (Ethiopia). We predicted that compared to pasture areas, crop areas (i) would be more challenging for geladas (prediction 1) and (ii) would have a greater impact on both aggressive and affiliative behavior, by reducing grooming time and enhancing competition (prediction 2). During January-May 2019 and December 2019-February 2020, we collected data (via scan, focal animal sampling, and video analyses) on direct human disturbance, external signs of pathologies and social behavior of 140 individuals from 14 one-male units and two all-male units. Animals experienced the highest level of human disturbance in crop areas (in line with prediction 1). Individuals from the groups preferentially frequenting crop areas showed the highest prevalence of external signs of pathologies consistent with chemical and biological contamination (alopecia/abnormally swollen parts). We collected 48 fecal samples. Samples from frequent crop users contained the highest rates of parasitic elements/gram (egg/larva/oocyst/cyst) from Entamoeba histolytica/dispar, a parasite common in human settlements of the Amhara region. In crop areas, subjects spent less time grooming but engaged in lower rates of intense aggression (in partial agreement with prediction 2). We speculate that the reduction in social behavior may be a tactic adopted by geladas to minimize the likelihood of detection and maximize food intake while foraging in crops.

Operando Study of Thermal Oxidation of Monolayer MoS2.

Monolayer MoS2 is a promising semiconductor to overcome the physical dimension limits of microelectronic devices. Understanding the thermochemical stability of MoS2 is essential since these devices generate heat and are susceptible to oxidative environments. Herein, the promoting effect of molybdenum oxides (MoO x ) particles on the thermal oxidation of MoS2 monolayers is shown by employing operando X-ray absorption spectroscopy, ex situ scanning electron microscopy and X-ray photoelectron spectroscopy. The study demonstrates that chemical vapor deposition-grown MoS2 monolayers contain intrinsic MoO x and are quickly oxidized at 100 °C (3 vol% O2/He), in contrast to previously reported oxidation thresholds (e.g., 250 °C, t ≤ 1 h in the air). Otherwise, removing MoO x increases the thermal oxidation onset temperature of monolayer MoS2 to 300 °C. These results indicate that MoO x promote oxidation. An oxide-free lattice is critical to the long-term stability of monolayer MoS2 in state-of-the-art 2D electronic, optical, and catalytic applications.

Efficacy of a Low-Dose Diosmin Therapy on Improving Symptoms and Quality of Life in Patients with Chronic Venous Disease: Randomized, Double-Blind, Placebo-Controlled Trial.

Chronic Venous Disease (CVD) is a common medical condition affecting up to 80% of the general population. Clinical manifestations can range from mild to more severe signs and symptoms that contribute to the impairment of the quality of life (QoL) of affected patients. Among treatment options, venoactive drugs such as diosmin are widely used in the symptomatic treatment in all clinical stages. The aim of this study is to determine the effectiveness of a new formulated diosmin in relieving symptoms and improving QoL in patients suffering from CVD. In this randomized, double-blind, placebo-controlled, multicenter clinical study, CVD patients with a Clinical-Etiology-Anatomy-Pathophysiology (CEAP) classification system between C2 and C4 were randomized to receive a bioavailable diosmin (as µsmin® Plus) 450 mg tablet once daily or a placebo for 8 weeks. Clinical symptoms and QoL were monitored using the measurement of leg circumference, visual analogue scale (VAS) for pain, Global Index Score (GIS) and Venous Clinical Severity Score (VCSS). A total of 72 subjects completed the study. From week 4, leg edema was significantly decreased in the active group (p < 0.001). An improvement in the VAS score was observed in the active group compared to placebo at the end of treatment (p < 0.05). GIS and VCSS scores were significantly improved in the active group at week 8 (p < 0.001). No treatment related-side effects were recorded. The results of this study showed that the administration of low-dose µsmin® Plus was safe and effective in relieving symptoms and improving QoL in subjects with CVD.

Tuning the electronic structure of Ag-Pd alloys to enhance performance for alkaline oxygen reduction.

Alloying is a powerful tool that can improve the electrocatalytic performance and viability of diverse electrochemical renewable energy technologies. Herein, we enhance the activity of Pd-based electrocatalysts via Ag-Pd alloying while simultaneously lowering precious metal content in a broad-range compositional study focusing on highly comparable Ag-Pd thin films synthesized systematically via electron-beam physical vapor co-deposition. Cyclic voltammetry in 0.1 M KOH shows enhancements across a wide range of alloys; even slight alloying with Ag (e.g. Ag0.1Pd0.9) leads to intrinsic activity enhancements up to 5-fold at 0.9 V vs. RHE compared to pure Pd. Based on density functional theory and x-ray absorption, we hypothesize that these enhancements arise mainly from ligand effects that optimize adsorbate-metal binding energies with enhanced Ag-Pd hybridization. This work shows the versatility of coupled experimental-theoretical methods in designing materials with specific and tunable properties and aids the development of highly active electrocatalysts with decreased precious-metal content.

Let's unite in play! Play modality and group membership in wild geladas.

Two of the main hypotheses put forth to explain the function of immature social play are the Social Skill Hypothesis and the Motor Training Hypothesis focussing on whether play can improve social competence to develop cooperative social networks or physical abilities to outcompete others, respectively. Here, we tested these hypotheses on a monkey species, the wild gelada (Theropithecus gelada) from the Kundi plateau, Ethiopia. This species is organized in bands divided in One-Male Units (OMUs), united only via social play. Immatures form 'play units' in which individuals from the same and different OMUs interact. We analysed the potential differences between inter- and intra-OMU play to verify which of the two hypotheses (Social Skill or Motor Training Hypothesis) best explains the function of play in geladas. We analysed 527 video-recorded social play sessions and found mixed support for both hypotheses. In agreement with the Social Skill Hypothesis, we found that play in geladas shows scarce social canalization being similarly distributed across age, sex and group membership. In line with the Motor Training Hypothesis, we detected higher levels of competition (shorter and more unbalanced sessions) in inter-OMU compared to intra-OMU play. Hence, in geladas play can be a tool for both the development of social relationships and the improvement of the physical skills necessary to cope with either future mates or competitors. In conclusion, neither hypothesis can be discarded and both hypotheses concur in explaining why immature geladas peculiarly form 'play units' embracing both ingroup and outgroup members.

PredyCLU: A prediction system for chronic leg ulcers based on fuzzy logic; part II-Exploring the arterial side.

Peripheral arterial disease (PAD) and its most severe form, critical limb ischaemia (CLI), are very common clinical conditions related to atherosclerosis and represent the major causes of morbidity, mortality, disability, and reduced quality of life (QoL), especially for the onset of ischaemic chronic leg ulcers (ICLUs) and the subsequent need of amputation in affected patients. Early identification of patients at risk of developing ICLUs may represent the best form of prevention and appropriate management. In this study, we used a Prediction System for Chronic Leg Ulcers (PredyCLU) based on fuzzy logic applied to patients with PAD. The patient population consisted of 80 patients with PAD, of which 40 patients (30 males [75%] and 10 females [25%]; mean age 66.18 years; median age 67.50 years) had ICLUs and represented the case group. Forty patients (100%) (27 males [67.50%] and 13 females [32.50%]; mean age 66.43 years; median age 66.50 years) did not have ICLUs and represented the control group. In patients of the case group, the higher was the risk calculated with the PredyCLU the more severe were the clinical manifestations recorded. In this study, the PredyCLU algorithm was retrospectively applied on a multicentre population of 80 patients with PAD. The PredyCLU algorithm provided a reliable risk score for the risk of ICLUs in patients with PAD.

Excited state charge distribution and bond expansion of ferrous complexes observed with femtosecond valence-to-core x-ray emission spectroscopy.

Valence-to-core x-ray emission spectroscopy (VtC XES) combines the sample flexibility and element specificity of hard x-rays with the chemical environment sensitivity of valence spectroscopy. We extend this technique to study geometric and electronic structural changes induced by photoexcitation in the femtosecond time domain via laser-pump, x-ray probe experiments using an x-ray free electron laser. The results of time-resolved VtC XES on a series of ferrous complexes [Fe(CN)2n(2, 2'-bipyridine)3-n]-2n+2, n = 1, 2, 3, are presented. Comparisons of spectra obtained from ground state density functional theory calculations reveal signatures of excited state bond length and oxidation state changes. An oxidation state change associated with a metal-to-ligand charge transfer state with a lifetime of less than 100 fs is observed, as well as bond length changes associated with metal-centered excited states with lifetimes of 13 ps and 250 ps.