Fluorescence enhancement of fungicide thiabendazole by van der Waals interaction with transition metal dichalcogenide nanosheets for highly specific sensors

Many molecules quench their fluorescence upon adsorption on surfaces. Herein we show that the interaction of thiabendazole, a widespread used fungicide of the benzimidazole family, with nanosheets of transition metal dichalcogenides, particularly of WS2, leads to a significant increase, more than a factor of 5, of the fluorescence yield. This surprising effect is rationalized by DFT calculations and found to be related to the inhibition of the intramolecular rotation between the benzimidazole and thiazole groups due to a bonding rigidization upon interaction with the MoS2 surface. This non-covalent adsorption leads to a redistribution of the molecular LUMO that blocks the non-radiative energy dissipation channel. This unusual behaviour does not operate either for other molecules of the same benzimidazole family or for other 2D materials (graphene or graphene oxide). Moreover, we found that a linear dependence of the emission with the concentration of thiabendazole in solution, which combined with the specificity of the process, allows the development of a highly sensitive and selective method towards thiabendazole determination that can be applied to real river water samples. An excellent detection limit of 2.7 nM, comparable to the best performing reported methods, is obtained with very good accuracy (Er ≤ 6.1%) and reproducibility (RSD ≤ 4.1%) in the concentration range assayedThe authors acknowledge financial support from the Spanish MINECO (MAT2017-85089-C2-1-R, MAT2017-85089-C2-2-R) and the EU via the ERC-Synergy Program (grant ERC-2013-SYG-610256 NANOCOSMOS) and Horizon 2020 Research and Innovation Program (Graphene Flagship-core2 – 785219) and the Comunidad Autónoma de Madrid (P2018/NMT-4349, TRANSNANOAVANSENS-CM and P2018/NMT-4367 FOTOART). J. I. M. acknowledges the support by the “Ramón y Cajal” Program of MINECO (grant RYC-2015-17730

A Systematic Review on the Association between Schizophrenia and Bipolar Disorder with Chronic Obstructive Pulmonary Disease

A systematic review aimed to investigate the association between schizophrenia and bipolar disorder and chronic obstructive pulmonary disease (COPD), its prevalence and incidence, potential factors associated with its occurrence and its impact on mortality among these patients. We performed the literature search in PubMed, Scopus and PsycInfo from inception to February 2022 and identified 19 studies: ten cross-sectional, 5 that included cross-sectional and longitudinal analyses, and 4 retrospective cohort studies. The reported prevalence of COPD ranged from 2.6% to 52.7% in patients with schizophrenia and between 3.0% and 12.9% in patients with bipolar disorder. Two studies reported an annual incidence of COPD of 2.21 cases/100 person-years in patients with schizophrenia and 2.03 cases/100 person-years in patients with bipolar disorder. Among the risk factors evaluated in three studies, only advanced age was consistently associated with the presence/occurrence of COPD in patients with schizophrenia and bipolar disorder; the role of tobacco consumption was not investigated in those three studies. According to two studies, the likelihood of mortality from COPD showed an over 3-fold increase in patients with schizophrenia and a 2-fold increase in those with bipolar disorder compared to the overall population; COPD was also associated with increased inpatient mortality. Available data indicate that COPD in patients with schizophrenia and bipolar disorder is a major public health problem. National and international health organizations should strive to specifically address this issue by creating awareness about this health problem and developing specific programs for screening and early intervention aimed to reduce the burden of COPD in these populations

Unveiling the collaborative effect at the cucurbit[8]urilMoS2 hybrid interface for electrochemical melatonin determination

Host-guest interactions are of paramount importance in supramolecular chemistry and in a wide range of applications. Particularly well known is the ability of cucurbit[n]urils (CB[n]) to selectively host small molecules. We show that the charge transfer and complexation capabilities of CB[n] are retained on the surface of 2D transition metal dichalcogenides (TMDs), allowing the development of efficient electrochemical sensing platforms. We unveil the mechanisms of host-guest recognition between the MoS2- CB[8] hybrid interface and melatonin (MLT), an important molecular regulator of vital constants in vertebrates. We find that CB[8] on MoS2 organizes the receptor portals perpendicularly to the surface, facilitating MLT complexation. This advantageous adsorption geometry is specific to TMDs and favours MLT electro-oxidation, as opposed to other 2D platforms like graphene, where one receptor portal is closed. This study rationalises the cooperative interaction in 2D hybrid systems to improve the efficiency and selectivity of electrochemical sensing platform

Tamoxifen disrupts the reproductive process in gilthead seabream males and modulates the effects promoted by 17alpha-ethynylestradiol

17α-ethynylestradiol (EE2), which is used in oral contraceptives and hormone replacement therapy, is a well documented estrogenic endocrine disruptor and an aquatic contaminant. In the present study, adult male specimens of the marine hermaphrodite teleost gilthead (Sparus aurata L.) were fed a diet containing tamoxifen (Tmx), an estrogen receptor ligand used in cancer therapy, alone or combined with EE2, for 25 days and then fed a commercial diet for a further 25 days (recovery period). The effects of short (5 days) and long (25 days) treatments on several reproductive and gonad immune parameters and the reversibility of the disruptive effects after the recovery period were examined. Our data showed that Tmx acted as an estrogenic endocrine disruptor as revealed by the increase in the hepatic transcription of the vitellogenin gene in males, the serum levels of 17β-estradiol and the gonad expression levels of the estrogen receptor α and G protein-coupled estrogen receptor genes, and the recruitment of leukocytes into the gonad, a well known estrogenic-dependent process in gilthead seabream males. On the other hand, Tmx also increased sperm concentration and motility as well as the serum levels of androgens and the expression levels of genes that codify for androgenic enzymes, while decreasing the expression levels of the gene that code for gonadal aromatase. When applied simultaneously, Tmx and EE2 could act in synergy or counteract, each other, depending on the parameter measured. The disruptive effect of EE2 and/or Tmx was not reversible after a 25 day recovery period.Postprin

Nectar yeasts of the Metschnikowia clade are highly susceptible to azole antifungals widely used in medicine and agriculture

The widespread use of azole antifungals in medicine and agriculture and the resulting long-persistent residues could potentially affect beneficial fungi. However, there is very little information on the tolerance of non-target environmental fungi to azoles. In this study, we assessed the susceptibility of diverse plant- and insect-associated yeasts from the Metschnikowia clade, including several ecologically important species, to widely used medical and agricultural azoles (epoxiconazole, imazalil, ketoconazole and voriconazole). A total of 120 strains from six species were tested. Minimum inhibitory concentrations (MICs) were determined by the EUCAST broth microdilution procedure after some necessary modifications were made. The majority of species tested were highly susceptible to epoxiconazole, ketoconazole and voriconazole (>95% of strains showed MICs ≤ 0.125 mg l). Most strains were also very susceptible to imazalil, although MIC values were generally higher than for the other azoles. Furthermore, certain Metschnikowia reukaufii strains displayed a 'trailing' phenotype (i.e. showed reduced but persistent growth at antifungal concentrations above the MIC), but this characteristic was dependent on test conditions. It was concluded that exposure to azoles may pose a risk for ecologically relevant yeasts from the Metschnikowia clade, and thus could potentially impinge on the tripartite interaction linking these fungi with plants and their insect pollinators.Peer Reviewe

Innovación, producción de acción e intencionalidad: notas para una teoría económica comprehensiva

La dinámica económica entendida como producción de instantes de realidad permite integrar tanto la dimensión inherentemente intencional de la acción como el carácter evolutivo de la economía. Cualquier consideración de un marco conceptual no dinámico (en un sentido sustantivo) acaba convirtiendo la racionalidad económica de los agentes en un mero cálculo lógico entre alternativas dadas, dando lugar a una economía entendida como tecnología de la elección. En este trabajo se integran intencionalidad e innovación en un marco analítico más comprehensivo que el de la teoría económica más convencional. A tal efecto esbozamos una teoría dinámica basada en una teoría de la producción de acción, especialmente de- dicada a enfatizar la naturaleza inédita de “lo elegible”. Como resultado, la dinámica económica es el proceso de generación, selección e intento de despliegue en interacción de planes de acción de los agentes y los productos (consecuencias) que resultan de esto. Entre estos productos resultantes se encuentran las novedades o innovaciones que transforman cualitativa y cuantitativamente el sistema económico.Economic dynamics understood as a process of production of instants of reality allows integrating within the same analytical framework the intentional dimension of action and the evolving nature of the economy. Any consideration of a non-dynamic conceptual framework (in a substantive sense) ends with agents’ economic rationality just becoming a mere logical calculation among given alternatives; that is, a conception of economics understood as a technology-of-choice. In this article we integrate intentio- nality and innovation in an analytical framework that is more comprehensive than the more conventional economic theory. For this purpose we outline a dynamic analytical framework based on a theory of the production-of-action that emphasizes the unique nature of the “choosable”. As a result, economic dynamics is the process of generation, selection and interactive deployment of agents’ action plans and products (consequences) that result from this social interaction. These products include the novelties or innovations that transform both qualitatively and quantitatively the economic system

17α‑ethynylestradiol prevents the natural male‑to‑female sex change in gilthead seabream (Sparus aurata L.)

Exposure to 17α-ethynylestradiol (EE2, 5 μg/g food) impairs some reproductive events in the protandrous gilthead seabream and a short recovery period does not allow full recovery. In this study, spermiating seabream males in the second reproductive cycle (RC) were fed a diet containing 5 or 2.5 μg EE2/g food for 28 days and then a commercial diet without EE2 for the remaining RC. Individuals were sampled at the end of the EE2 treatment and then at the end of the RC and at the beginning of the third RC, 146 and 333 days after the cessation of treatment, respectively. Increased hepatic transcript levels of the gene coding for vitellogenin (vtg) and plasma levels of Vtg indicated both concentrations of EE2 caused endocrine disruption. Modifications in the histological organization of the testis, germ cell proliferation, plasma levels of the sex steroids and pituitary expression levels of the genes coding for the gonadotropin β-subunits, fshβ and lhβ were detected. The plasma levels of Vtg and most of the reproductive parameters were restored 146 days after treatments. However, although 50% of the control fish underwent sex reversal as expected at the third RC, male-to female sex change was prevented by both EE2 concentrations.Ministerio de Ciencia e Innovación and FEDER (AGL2014-53167-C3-1R, -2-R; AGL2017-85978-C2-1-R; RTI2018-096625-B-C33) and the Fundación Séneca (CARM) (19883/GERM/15).Versión del editor2,92