Microwave-assisted functionalization of carbon nanohorns with oligothiophene units with SERS activity

[EN] Carbon nanohorns have been functionalized with oligothiophene unitsviathe 1,3-dipolar cycloaddition reaction under microwave irradiation and solvent-free conditions. A dramatic Raman enhancement was found for one of the synthesized derivatives. Experimental andin silicostudies helped to understand the enhancement, attributed to the modification of electromagnetic fields upon functionalization at the tip of the nanostructures.This work was supported by the Iberdrola Foundation (CONV120313), the Spanish Ministerio de Economia y Competitividad (CTQ2017-88158-R), the Junta de Comunidades de Castilla-La Mancha (SBPLY/17/180501/000204) and FEDER-JCCM (UNCM13-1E-1663). The work at the University of Malaga was funded by the MICINN (PID2019-110305GB-I00) and Junta de Andalucia (P09FQM-4708) projects. M. I. L. acknowledges MINECO for her Juan de la Cierva-formacion grant (FJCI-2016-29593). The authors acknowledge the computer resources, technical expertise, and assistance provided by the Supercomputing and Bioinformatics centre of the University of Malaga.Iglesias, D.; Guerra, J.; Lucío, MI.; González-Cano, RC.; Lopez Navarrete, JT.; Ruiz Delgado, MC.; Vázquez, E.... (2020). Microwave-assisted functionalization of carbon nanohorns with oligothiophene units with SERS activity. Chemical Communications. 56(63):8948-8951. https://doi.org/10.1039/D0CC03496G89488951566

Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes

New stilbenoid and thiophenic compounds terminally functionalized with donor–donor, acceptor–acceptor, or donor–acceptor moieties and possessing a central [2.2]­paracyclophane unit have been prepared, and their properties interpreted in terms of through-bond and through space π-electron delocalization (i.e., π-conjugations). Based on photophysical data, their excited-state properties have been described with a focus on the participation of the central [2.2]­paracyclophane in competition with through-bond conjugation in the side arms. To this end, two-photon and one-photon absorption and emission spectroscopy, as a function of temperature, solvent polarity, and pressure in the solid state have been recorded. Furthermore, charge delocalization through the [2.2]­paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both “intermolecular” excitation and charge delocalizations in [2.2]­paracyclophane molecules is shown which can serve as models of charge and exciton migration in organic semiconductors

Cabbage and fermented vegetables : From death rate heterogeneity in countries to candidates for mitigation strategies of severe COVID-19

Large differences in COVID-19 death rates exist between countries and between regions of the same country. Some very low death rate countries such as Eastern Asia, Central Europe, or the Balkans have a common feature of eating large quantities of fermented foods. Although biases exist when examining ecological studies, fermented vegetables or cabbage have been associated with low death rates in European countries. SARS-CoV-2 binds to its receptor, the angiotensin-converting enzyme 2 (ACE2). As a result of SARS-CoV-2 binding, ACE2 downregulation enhances the angiotensin II receptor type 1 (AT(1)R) axis associated with oxidative stress. This leads to insulin resistance as well as lung and endothelial damage, two severe outcomes of COVID-19. The nuclear factor (erythroid-derived 2)-like 2 (Nrf2) is the most potent antioxidant in humans and can block in particular the AT(1)R axis. Cabbage contains precursors of sulforaphane, the most active natural activator of Nrf2. Fermented vegetables contain many lactobacilli, which are also potent Nrf2 activators. Three examples are: kimchi in Korea, westernized foods, and the slum paradox. It is proposed that fermented cabbage is a proof-of-concept of dietary manipulations that may enhance Nrf2-associated antioxidant effects, helpful in mitigating COVID-19 severity.Peer reviewe

Nrf2-interacting nutrients and COVID-19 : time for research to develop adaptation strategies

There are large between- and within-country variations in COVID-19 death rates. Some very low death rate settings such as Eastern Asia, Central Europe, the Balkans and Africa have a common feature of eating large quantities of fermented foods whose intake is associated with the activation of the Nrf2 (Nuclear factor (erythroid-derived 2)-like 2) anti-oxidant transcription factor. There are many Nrf2-interacting nutrients (berberine, curcumin, epigallocatechin gallate, genistein, quercetin, resveratrol, sulforaphane) that all act similarly to reduce insulin resistance, endothelial damage, lung injury and cytokine storm. They also act on the same mechanisms (mTOR: Mammalian target of rapamycin, PPAR gamma:Peroxisome proliferator-activated receptor, NF kappa B: Nuclear factor kappa B, ERK: Extracellular signal-regulated kinases and eIF2 alpha:Elongation initiation factor 2 alpha). They may as a result be important in mitigating the severity of COVID-19, acting through the endoplasmic reticulum stress or ACE-Angiotensin-II-AT(1)R axis (AT(1)R) pathway. Many Nrf2-interacting nutrients are also interacting with TRPA1 and/or TRPV1. Interestingly, geographical areas with very low COVID-19 mortality are those with the lowest prevalence of obesity (Sub-Saharan Africa and Asia). It is tempting to propose that Nrf2-interacting foods and nutrients can re-balance insulin resistance and have a significant effect on COVID-19 severity. It is therefore possible that the intake of these foods may restore an optimal natural balance for the Nrf2 pathway and may be of interest in the mitigation of COVID-19 severity

Rising rural body-mass index is the main driver of the global obesity epidemic in adults

Body-mass index (BMI) has increased steadily in most countries in parallel with a rise in the proportion of the population who live in cities . This has led to a widely reported view that urbanization is one of the most important drivers of the global rise in obesity . Here we use 2,009\ua0population-based studies, with measurements of height and weight in more than 112\ua0million adults, to report national, regional and global trends in mean\ua0BMI segregated by place of residence (a rural or urban area) from 1985 to 2017. We show that, contrary to the dominant paradigm, more than 55% of the global rise in mean BMI from 1985 to 2017—and more than 80% in\ua0some low- and middle-income regions—was due to increases in BMI in rural areas. This large contribution stems from the fact that, with the exception of women in sub-Saharan Africa, BMI is increasing at the same rate or faster in rural areas than in cities\ua0in low- and middle-income regions. These trends have in turn resulted in a closing—and in some countries reversal—of the gap in BMI between urban and rural areas in low- and middle-income countries, especially for women. In high-income and industrialized countries, we noted a persistently higher rural BMI, especially for women. There is an urgent need for an integrated approach to rural nutrition that enhances financial and physical access to healthy foods, to avoid replacing the rural undernutrition disadvantage in poor countries with a more general malnutrition disadvantage that entails excessive consumption of low-quality calories

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

Structural implications of ring shape, dimension, and metal atom insertion in nanosized cyclic oligothiophenes : joint Raman and density functional theory study

This paper reports on a combined spectroscopic and density functional theory study on a series of cyclo(diacetylenes-oligothiophenes) with different shapes and dimensions. The case of a macrocycle fragmented by the insertion of Pt metallic atoms is illustrated as well. The analysis covers the neutral and oxidized samples. A full assignment of the spectra has been proposed, supported by BP86/cc-pVDZ theoretical calculations. Ring shape and molecular dimension have been related with the C[Double Bond]C/C\ufffdC structural parameters and Raman wave numbers. Platinum atom insertion within the acetylene spacer seems to soften ring strain owing to the rupture of the strained circular shape. Oxidation causes an overall downshift of the Raman wave numbers likely due to the skeletal relaxation of CC conjugated path, while the ring shape of each macrocycle is conserved upon oxidation.Peer reviewed: YesNRC publication: Ye

Enantiopure, Monodisperse Alleno-acetylenic Cyclooligomers: Effect of Symmetry and Conformational Flexibility on the Chiroptical Properties of Carbon-Rich Compounds

Enantiopure, monodisperse alleno-acetylenic cyclooligomers were synthesized. The single-crystal x-ray structures of the cyclic trimer and hexamer were resolved, providing insights into the symmetry of these mols. Electronic CD (ECD), ORD, Raman spectroscopy, and vibrational CD (VCD) data were analyzed with the aid of theor. calcns. This multidimensional approach ultimately provided general guidelines that are useful for designing carbon-rich compds. with intense chiroptical properties