Electrocatalytic CO2 Reduction with a Binuclear Bis-Terpyridine Pyrazole-Bridged Cobalt Complex.

A pyrazole-based ligand substituted with terpyridine groups at the 3 and 5 positions has been synthesized to form the dinuclear cobalt complex 1, that electrocatalytically reduces carbon dioxide (CO2 ) to carbon monoxide (CO) in the presence of Brønsted acids in DMF. Chemical, electrochemical and UV-vis spectro-electrochemical studies under inert atmosphere indicate pairwise reduction processes of complex 1. Infrared spectro-electrochemical studies under CO2 and CO atmosphere are consistent with a reduced CO-containing dicobalt complex which results from the electroreduction of CO2 . In the presence of trifluoroethanol (TFE), electrocatalytic studies revealed single-site mechanism with up to 94 % selectivity towards CO formation when 1.47 M TFE were present, at -1.35 V vs. Saturated Calomel Electrode in DMF (0.39 V overpotential). The low faradaic efficiencies obtained (<50 %) are attributed to the generation of CO-containing species formed during the electrocatalytic process, which inhibit the reduction of CO2 .

Enhanced Dihydrogen Activation by Mononuclear Iridium(II) Compounds: A Mechanistic Study.

The organometallic chemistry of 4d and 5d transition metals has been vastly dominated by closed-shell states. The reactivity of their metalloradical species is though remarkable, albeit yet poorly understood and with limited mechanistic investigations available. In this work we report the synthesis and characterization of two mononuclear IrII species, including the first dinitrogen adduct. These compounds activate dihydrogen at a dissimilar rate, in the latter case several orders of magnitude faster than its IrI precursor. A combined experimental/computational investigation to ascertain the mechanism of this transformation in IrII compounds is reported.

Perceived Intensity and Palatability of Fatty Culinary Preparations is Associated with Individual Fatty Acid Detection Threshold and the Fatty Acid Profile of Oils Used as Ingredients.

The term oleogustus was recently proposed to describe a sixth basic taste that could guide preference for fatty foods and dishes to an extent. However, experimental data on food preference based on fatty acid (FA) content is scarce. Our aim was to examine the role of FA profile of oils and preparations as well as FA sensory thresholds on the palatability of salty and sweet culinary preparations representative of traditional Spanish Mediterranean cooking. In this study, we used three oils with similar texture and odor profile but different in their FA composition (saturated, monounsaturated, and polyunsaturated) and compared subjects in regard to their FA detection threshold and perceived pleasantness and intensity. Our results indicate that whereas saturated FAs cannot be detected at physiological concentrations, individuals can be categorized as tasters and nontasters, according to their sensory threshold to linoleic acid, which is negatively associated with perceived intensity (r = -0.393, P < 0.001) but positively with palatability (r = 0.246, P = 0.018). These differences may be due to a possible response to a fat taste. This sixth taste, or oleogustus. would allow establishing differences in taste intensity/palatability considering the FA profile of the culinary preparations. Given that tasters can detect linoleic and oleic acid at lower concentrations than nontasters, a greater amount of unsaturated FAs in culinary preparations could provoke an unpleasant experience. This finding could be relevant in the context of the culinary sector and to further our understanding of food preference and eating behavior.

Evidence for Genuine Bimetallic Frustrated Lewis Pair Activation of Dihydrogen with Gold(I)/Platinum(0) Systems.

Invited for the cover of this issue is the group of Joaquín López-Serrano and Jesús Campos at the Consejo Superior de Investigaciones Científicas and the University of Sevilla. The image depicts the importance of balancing the degree of frustration/interaction in the splitting of H2 by AuI /Pt0 . Read the full text of the article at 10.1002/chem.201905793.

Evidence for Genuine Bimetallic Frustrated Lewis Pair Activation of Dihydrogen with Gold(I)/Platinum(0) Systems.

A joint experimental/computational effort to elucidate the mechanism of dihydrogen activation by a gold(I)/platinum(0) metal-only frustrated Lewis pair (FLP) is described herein. The drastic effects on H2 activation derived from subtle ligand modifications have also been investigated. The importance of the balance between bimetallic adduct formation and complete frustration has been interrogated, providing for the first time evidence for genuine metal-only FLP reactivity in solution. The origin of a strong inverse kinetic isotopic effect has also been clarified, offering further support for the proposed bimetallic FLP-type cleavage of dihydrogen.

Effect of physiological factors, pathologies, and acquired habits on the sweet taste threshold: A systematic review and meta-analysis.

Sweet taste perception is a key factor in the establishment of the food pattern with nonstatic thresholds. Indeed, taste sensitivity can be influenced by physiological factors (age and sex), pathologies (obesity and type 2 diabetes mellitus), and acquired habits (tobacco and alcohol consumption). In order to elucidate how these variables influence the sucrose detection threshold (DT) and recognition threshold (RT), a systematic review and meta-analysis of the relevant literature were performed. After a comprehensive search in the PubMed and Scopus databases, a total of 48 studies were qualitatively considered, and 44 were meta-analyzed. The factors of aging (standard mean difference [SMD]: -0.46; 95% confidence interval (CI), -0.74 to -0.19; I2 : 73%; Tau2 : 0.18) and type 2 diabetes mellitus (SMD: 0.30; 95% CI, 0.06 to 0.55; I2 : 0%; Tau2 : 0.00) were found to significantly increase the sucrose RT, whereas the DT only increased in subjects with a higher body mass index (SMD: 0.58; 95% CI, 0.35 to 0.82; I2 : 0%; Tau2 : 0.00). No effects of sex and tobacco smoking were found, and associations with alcohol consumption could not be assessed, as it was included as a variable in only one study. Feasible mechanisms underlying changes in sucrose thresholds include the modulation of hormones involved in energy and body weight homeostasis, taste bud abundance, taste brain signaling, and the gut-brain axis. The present work provides insights into the variables that should be considered when assessing sweet taste sensitivity, discusses the mechanisms underlying differences in sweet taste, and highlights the need for further research in the field of personalized nutrition.

Cannabinoids, Chemical Senses, and Regulation of Feeding Behavior.

The herb Cannabis sativa has been traditionally used in many cultures and all over the world for thousands of years as medicine and recreation. However, because it was brought to the Western world in the late 19th century, its use has been a source of controversy with respect to its physiological effects as well as the generation of specific behaviors. In this regard, the CB1 receptor represents the most relevant target molecule of cannabinoid components on nervous system and whole-body energy homeostasis. Thus, the promotion of CB1 signaling can increase appetite and stimulate feeding, whereas blockade of CB1 suppresses hunger and induces hypophagia. Taste and flavor are sensory experiences involving the oral perception of food-derived chemicals and drive a primal sense of acceptable or unacceptable for what is sampled. Therefore, research within the last decades focused on deciphering the effect of cannabinoids on the chemical senses involved in food perception and consequently in the pattern of feeding. In this review, we summarize the data on the effect of cannabinoids on chemical senses and their influences on food intake control and feeding behavior.

Role of Endocannabinoids on Sweet Taste Perception, Food Preference, and Obesity-related Disorders.

The prevalence of obesity and obesity-related disorders such as type 2 diabetes (T2D) and metabolic syndrome has increased significantly in the past decades, reaching epidemic levels and therefore becoming a major health issue worldwide. Chronic overeating of highly palatable foods is one of the main responsible aspects behind overweight. Food choice is driven by food preference, which is influenced by environmental and internal factors, from availability to rewarding properties of food. Consequently, the acquisition of a dietary habit that may lead to metabolic alterations is the result of a learning process in which many variables take place. From genetics to socioeconomic status, the response to food and how this food affects energy metabolism is heavily influenced, even before birth. In this work, we review how food preference is acquired and established, particularly as regards sweet taste; towards which flavors and tastes we are positively predisposed by our genetic background, our early experience, further lifestyle, and our surroundings; and, especially, the role that the endocannabinoid system (ECS) plays in all of this. Ultimately, we try to summarize why this system is relevant for health purposes and how this is linked to important aspects of eating behavior, as its function as a modulator of energy homeostasis affects, and is affected by, physiological responses directly associated with obesity.

Differential cell growth/apoptosis behavior of 13-hydroxyoctadecadienoic acid enantiomers in a colorectal cancer cell line.

Cyclooxygenases (COXs) and lipoxygenases (LOXs) are important enzymes that metabolize arachidonic and linoleic acids. Various metabolites generated by the arachidonic acid cascade regulate cell proliferation, apoptosis, differentiation, and senescence. Hydroxyoctadecadienoic acids (HODEs) are synthesized from linoleic acid, giving two enantiomeric forms for each metabolite. The aim was to investigate the effect of 13-HODE enantiomers on nondifferentiated Caco-2 cell growth/apoptosis. Our results indicate that 13(S)-HODE decreases cell growth and DNA synthesis of nondifferentiated Caco-2 cells cultured with 10% fetal bovine serum (FBS). Moreover, 13(S)-HODE showed an apoptotic effect that was reduced in the presence of a specific peroxisome proliferator-activated receptor-γ (PPARγ) antagonist. In addition, we observed that 13(S)-HODE but not 13(R)-HODE is a ligand to PPARγ, confirming the implication of this nuclear receptor in 13(S)-HODE actions. In contrast, 13(R)-HODE increases cell growth and DNA synthesis in the absence of FBS. 13(R)-HODE interaction with BLT receptors activates ERK and CREB signaling pathways, as well as PGE2 synthesis. These results suggest that the proliferative effect of 13(R)-HODE could be due, at least in part, to COX pathway activation. Thus both enantiomers use different receptors and have contrary effects. We also found these differential effects of 9-HODE enantiomers on cell growth/apoptosis. Therefore, the balance between (R)-HODEs and (S)-HODEs in the intestinal epithelium could be important to its cell growth/apoptosis homeostasis.

Bitter taste receptors: Key target to understand the effects of polyphenols on glucose and body weight homeostasis. Pathophysiological and pharmacological implications.

Experimental and clinical research has reported beneficial effects of polyphenol intake on high prevalent diseases such as type 2 diabetes and obesity. These phytochemicals are ligands of taste 2 receptors (T2Rs) that have been recently located in a variety of organs and extra-oral tissues. Therefore, the interaction between polyphenol and T2Rs in brain structures can play a direct effect on appetite/satiety regulation and food intake. T2Rs are also expressed along the digestive tract, and their interaction with polyphenols can induce the release of gastrointestinal hormones (e.g., ghrelin, GLP-1, CCK) influencing appetite, gastrointestinal functionally, and glycemia control. Intestinal microbiota can also influence on network effects of polyphenols-T2Rs interaction and vice versa, impacting innate immune responses and consequently on gut functionally. Furthermore, polyphenols binding to T2Rs present important effects on adipose tissue metabolism. Interestingly, T2R polymorphism could, at least partially, explain the inter-individual variability of the effects of polyphenols on glucose and body weight homeostasis. Together, these factors can contribute to understand the beneficial effects of polyphenol-rich diets but also might aid in identifying new pharmacological pathway targets for the treatment of diabetes and obesity.

Assessing the social impacts of the COVID-19 crisis using phone helplines. The case of the Balearic Islands, Spain.

Background: Crises and health policies to tackle them can increase health inequalities. We explored the scope and usefulness of helplines set up during the COVID-19 crisis and characterised the vulnerability of their users. This study explored the geographic and socioeconomic effects of the telephone helplines set up by the Balearic Islands Government and aimed to characterise the vulnerability of their users. Methods: Telephonic survey combined with a geographical analysis of a sample of calls made between 15th of March and 30th of June of 2020 to five helplines: COVID-19 general information; psychological, social (minimum vital income), labour (temporary employment regulation), and housing (rental assistance) helps. The questionnaire included sociodemographic and housing characteristics, type of problem, and if it was solved or not. We used multinomial regression to explore factors associated with having solved the problem. We calculated the standardised rate of calls by municipality using Chi-squared and z-test to test differences. Results: 1,321 interviews from 2,678 selected (231 excluded, 608 untraceable, and 518 refusals). 63.8% of women, 48.7% were born in another country. They had no internet at home in 3.1%, only on the phone in 17.3%. The 23.5% had no income at home. The Problem was solved in 25.4%, and partly in 30.9%. Factors associated with not solving the problem were not having income at home (p = 0.021), labour (p = 0.008), economic (p = 0.000) or housing (p = 0.000) problems. People from 55 of 67 municipalities did at least one call. The highest rates of calls were from coastal tourist municipalities. Conclusion: Helplines reached most of the territory of the Balearic Islands and were used mainly in tourist municipalities. It probably has not been helpful for families with more significant deprivation. Digital inequalities have emerged.

Improving drug discovery through parallelism.

Compound identification in ligand-based virtual screening is limited by two key issues: the quality and the time needed to obtain predictions. In this sense, we designed OptiPharm, an algorithm that obtained excellent results in improving the sequential methods in the literature. In this work, we go a step further and propose its parallelization. Specifically, we propose a two-layer parallelization. Firstly, an automation of the molecule distribution process between the available nodes in a cluster, and secondly, a parallelization of the internal methods (initialization, reproduction, selection and optimization). This new software, called pOptiPharm, aims to improve the quality of predictions and reduce experimentation time. As the results show, the performance of the proposed methods is good. It can find better solutions than the sequential OptiPharm, all while reducing its computation time almost proportionally to the number of processing units considered.

Personal exposure from free Wi-Fi hotspots in downtown Mexico City.

In 2019, the Government of Mexico City implemented actions that allowed citizens to approach a free Wi-Fi hotspot, where more than 13000 points have been installed throughout the city. In this work, we present the results of the measurements of personal exposure to Radiofrequency Electromagnetic Fields carried out in Plaza de la Constitución, better known as Zócalo located in the center of Mexico City. The measurements were taken by one of the researchers while walking on a weekday morning and afternoon, in different microenvironments (on the street, on public transport: subway, at the Zócalo, and finally, at home). We also carry out spot measurements in the center of the Zócalo. Subsequently, we carried out a comparative analysis of the different microenvironments, through box plot and violin plot, and we elaborate georeferenced and interpolated maps with intensity levels through the Kriging method, using the Geographic Information System. The Kriging interpolation gives us a good visualization of the spatial distribution of RF-EMF exposure in the study area, showing the highest and lowest intensity levels. The mean values recorded at the measured points in the Zócalo were 326 µW/m2 in the 2.4- to 2.5-GHz Wi-Fi band and 2370 µW/m2 in the 5.15- to 5.85-GHz Wi-Fi band. In the case of the mean values recorded on the street, they were 119 µW/m2 in the 2.4- to 2.5-GHz frequency band and 31.8 µW/m2 in the 5.15- to 5.85-GHz frequency band, like the values recorded at home, 122 µW/m2 and 33.9 µW/m2, respectively. All values are well below the reference levels established by the International Commission on Non-Ionizing Radiation Protection.

Acute Retinal Necrosis: Experience in a Reference Center in Santander - Colombia.

INTRODUCTION: Acute retinal necrosis (ARN) is a severe eye disease demanding swift treatment to prevent blindness. Early action involving antiviral medications and corticosteroids is crucial for optimal visual outcomes. OBJECTIVE: We present an ARN case series showcasing treatment experience and results. METHODOLOGY: Patients diagnosed with ARN based on SUN Working Group 2021 criteria were included; all underwent comprehensive eye exams, PCR analysis, and imaging. RESULTS: Eight patients were studied; PCR confirmed ARN in six. Induction treatment, either oral valacyclovir (5/8) or intravenous acyclovir (3/8), lasted 10-14 days. Maintenance included oral valacyclovir (6/8), oral valganciclovir (2/8) for six months, along with intravitreal ganciclovir. Visual outcomes were similar for oral and intravenous therapies; poor baseline acuity and macular involvement tend to result in a worse final acuity. CONCLUSIONS: Swift treatment is vital to ARN management. Our findings emphasize effective treatment strategies' role in visual prognosis. ABBREVIATIONS: ACV: Acyclovir; BCVA: Best Corrected Visual Acuity; CMV: Cytomegalovirus; EBV: Epstein Barr Virus; FTA-ABS: Fluorescent treponemal antibody absorption test; HSV 1-2: Herpes simplex virus 1-2; HIV: Human Immunodeficiency Virus; IV-ACV: Intravenous- Acyclovir; PCR: Polymerase Chain Reaction;Tg: Toxoplasma gondii; VZV: Varicella Zoster Virus; VCV: Valacyclovir; VDRL: Venereal disease research laboratory test.

Drosophila SPG12 ortholog, reticulon-like 1, governs presynaptic ER organization and Ca2+ dynamics.

Neuronal endoplasmic reticulum (ER) appears continuous throughout the cell. Its shape and continuity are influenced by ER-shaping proteins, mutations in which can cause distal axon degeneration in Hereditary Spastic Paraplegia (HSP). We therefore asked how loss of Rtnl1, a Drosophila ortholog of the human HSP gene RTN2 (SPG12), which encodes an ER-shaping protein, affects ER organization and the function of presynaptic terminals. Loss of Rtnl1 depleted ER membrane markers at Drosophila presynaptic motor terminals and appeared to deplete narrow tubular ER while leaving cisternae largely unaffected, thus suggesting little change in resting Ca2+ storage capacity. Nevertheless, these changes were accompanied by major reductions in activity-evoked Ca2+ fluxes in the cytosol, ER lumen, and mitochondria, as well as reduced evoked and spontaneous neurotransmission. We found that reduced STIM-mediated ER-plasma membrane contacts underlie presynaptic Ca2+ defects in Rtnl1 mutants. Our results show the importance of ER architecture in presynaptic physiology and function, which are therefore potential factors in the pathology of HSP.

Resveratrol metabolites have an antiproliferative effect on intestinal epithelial cancer cells.

Trans-resveratrol (RV) is an active polyphenol with numerous physiological properties including antitumour activity, especially in colon cancer. RV is metabolized in the intestine and then in the liver to sulphated and glucuronidated forms that are exported to target organs. After exerting their effects, they are eliminated in the urine and stools. There are few and contradictory findings on the biological effects of RV metabolites. On the basis of RV metabolism, we selected three metabolites RV 3-O-sulphate, RV 3-O-glucuronide and RV 4'-O-glucuronide, and studied their effects on cell growth inhibition, the cell cycle and apoptosis using human adenocarcinoma cell line (Caco-2 cell) cultures. Our results show that RV metabolites have an antioxidant activity similar to that RV. Moreover, all metabolites inhibited cell growth in a concentration-dependent manner as well as [(3)H] thymidine incorporation. Furthermore, we observed an increase in the percentage of cell in G0/G1 phase induced by RV metabolite treatments, as well as the induction of apoptosis. On the basis of our results we propose, for the first time, that RV metabolites remain active after their biosynthesis, contributing to the health benefits attributed previously only to RV. These metabolites are a potential target for more research into the prevention and treatment of colon cancer.

Small molecule activation with bimetallic systems: a landscape of cooperative reactivity.

There is growing interest in the design of bimetallic cooperative complexes, which have emerged due to their potential for bond activation and catalysis, a feature widely exploited by nature in metalloenzymes, and also in the field of heterogeneous catalysis. Herein, we discuss the widespread opportunities derived from combining two metals in close proximity, ranging from systems containing multiple M-M bonds to others in which bimetallic cooperation occurs even in the absence of M⋯M interactions. The choice of metal pairs is crucial for the reactivity of the resulting complexes. In this context, we describe the prospects of combining not only transition metals but also those of the main group series, which offer additional avenues for cooperative pathways and reaction discovery. Emphasis is given to mechanisms by which bond activation occurs across bimetallic structures, which is ascribed to the precise synergy between the two metal atoms. The results discussed herein indicate a future landscape full of possibilities within our reach, where we anticipate that bimetallic synergism will have an important impact in the design of more efficient catalytic processes and the discovery of new catalytic transformations.

Corrigendum: LanB1 Cooperates With Kon-Tiki During Embryonic Muscle Migration in Drosophila.

[This corrects the article DOI: 10.3389/fcell.2021.749723.].

Discrimination of sweet wines partially fermented by two osmo-ethanol-tolerant yeasts by gas chromatographic analysis and electronic nose.

Some special sweet wines are obtained by partial fermentation of musts from off-vine dried grapes containing large amounts of sugars. This process is very slow and subject to serious stop problems that can be avoided by using osmo-ethanol-tolerant yeasts. Musts containing 371g/l of sugars were partially fermented with selected Saccharomyces cerevisiae strains, X4 and X5, to 12% (v/v) and the wines obtained with X5 exhibited a higher volatile acidity but lower concentrations of higher alcohols, carbonyl compounds and polyols than those obtained with X4. A principal component analysis (PCA) of the data provided by an electronic nose (E-nose) afforded discrimination between fermented and unfermented musts, but not between wines obtained with X4 or X5. The PCA applied to the major volatile compounds and polyols shows similar results, but a clear discrimination between wines is obtained by removing the polyols glycerol and 2,3-butanediol from the PCA.

The Association between Trainer Expertise and Changes in Adolescent Symptomatology in an Evidence-Based Family Prevention Programme.

PURPOSE: The aim of this study is to assess whether the outcomes of implementations of the Universal Strengthening Families Program (SFP 11-14) are linked to the competences or specific skills of the trainers of social field who gave them. METHOD: The analyzed data was based on ratings awarded by the 174 mothers participating in the SFP 11-14. By conducting a K-means cluster analysis, significant groups were identified, based on the ratings awarded to the trainers. RESULTS/DISCUSSION: A comparison of the clusters led to the identification of significant differences between cluster 2 (trainers with limited skills) and the other clusters in terms of changes in the children's symptoms after participating in the SFP 11-14. Trainers with limited skills were associated with fewer changes in the symptomatology. It highlights the importance of proficient trainers in programme outcomes, and it could serve as a guide for the public social work in the design of EBP.