Coordination Cages as a Scaffold for Permanently Porous Liquids

Porosity is a property that is conventionally associated with solids. While liquids can have transient pores, these cavities exist as temporary voids between the molecules of the liquid. The idea of permanently porous liquids combines the porosity of solids with the fluid properties of liquids by engineering intrinsic porosity into the liquid state. This class of materials shows potential in applications such as extractions and gas separations. We present the first adaptation of coordination cages into porous liquids by functionalizing a series coordination cages of different sizes and structures with alkylimidazolium and PEG-imidazolium moieties. The alkylimidazolium-functionalized cages showed increased solubility in similarly structured ionic liquids, yielding a Type II porous liquid. The PEG-imidazolium-functionalized cages were liquid at room temperature and acted as Type I porous liquids. Of these cages, a liquid Zn(II)4L4 tetrahedral capsule was chosen for additional characterization and applications. Rheological and thermal analysis of this liquid cage confirmed its fluidity. Positron annihilation lifetime spectroscopy indicated that the host pores remained empty under solvent-free conditions. This liquid cage was then used for host-guest experiments both in solution and in the neat state. The porous liquid was shown to encapsulate small alcohols shape-selectively, with a preference for alcohols with more branching. The liquid cage also dissolved and encapsulated three different chlorofluorocarbons. Additionally, we also present the first hetero-cage, which we define to be a coordination cage that is charge-balanced by a second, different cage of opposite charge. A hetero-cage was synthesized by charge-balancing a liquid coordination cage with +20 charge with 5 equivalents of a solid anionic cage with -4 charge. The resulting material was characterized by NMR, which confirmed that the cages were charge-balancing each other in the absence of additional counterions. Thermal analysis of hetero-cages indicated that the material was comprised of a solid suspension of the anionic cage in the liquid cationic cage, and that the phase change behaviors of the parent cages are preserved in the hetero-cage.Funded by the UK Engineering and Physical Sciences Research Council

Dynamic GATA4 enhancers shape the chromatin landscape central to heart development and disease.

How stage-specific enhancer dynamics modulate gene expression patterns essential for organ development, homeostasis and disease is not well understood. Here, we addressed this question by mapping chromatin occupancy of GATA4--a master cardiac transcription factor--in heart development and disease. We find that GATA4 binds and participates in establishing active chromatin regions by stimulating H3K27ac deposition, which facilitates GATA4-driven gene expression. GATA4 chromatin occupancy changes markedly between fetal and adult heart, with a limited binding sites overlap. Cardiac stress restored GATA4 occupancy to a subset of fetal sites, but many stress-associated GATA4 binding sites localized to loci not occupied by GATA4 during normal heart development. Collectively, our data show that dynamic, context-specific transcription factors occupancy underlies stage-specific events in development, homeostasis and disease

The Therapy of Desire in Times of Crisis: Lessons Learned from Buddhism and Stoicism

Desire is an important philosophical topic that deeply impacts everyday life. Philosophical practice is an emerging trend that uses philosophical theories and methods as a guide to living a eu‐ daimonic life. In this paper, we define desire philosophically and compare different theories of desire in specific Eastern and Western traditions. Based on the Lacanian conceptual–terminological triad of “Need‐Demand‐Desire”, the research of desire is further divided into three dimensions, namely, the subject of desire, the object of desire, and the desire itself. The concept of desire is then an‐ alyzed from this triad and these three dimensions through different philosophical theories. This paper selects Buddhism as the representative of Eastern tradition, and Stoicism as the representative of the West, paying special attention to Stoicism’s “spiritual exercises” following Pierre Hadot. By exploring and comparing the Buddhist paths to liberation from suffering (i.e., the Four Noble Truths and the Noble Eightfold Path) and the two theoretical pillars in Stoicism (i.e., the notions of “living according to nature” and “the dichotomy of control”), practical guidance is then provided for un‐ derstanding and regulating desire in times of crisis. This understanding and regulation of desire constitutes a philosophical therapy for today’s troubles, particularly those caused by excessive or irrational desires

Potential health claims of durum and bread wheat flours as functional ingredients

Wheat is an important cereal with a key role in human nutrition. In this study, dietary fiber (DF) and arabinoxylans of di erent durum (Triticum turgidum ssp. Durum L.) and bread (Triticum aestivum L.) wheat flours were analyzed in order to point out their potential nutritional and health claims allege according to the current European regulation (Regulation (EU) No 432/2012). Moreover, other bioactive compounds (phenolics and tocopherols) were quantified as a first approach to their phytochemical composition in the analyzed wheat varieties. DF was analyzed following AOAC enzymatic-gravimetric methods; arabinoxylans and total phenols were quantified by colorimetric methods; tocopherols were determined by HPLC; antioxidant activity was evaluated using three di erent in vitro assays. Insoluble DF was the prevailing fraction in all analyzed samples. Water extractable arabinoxylans were higher in durum wheat flours. Whole flours contained higher total phenolics compounds. Alpha-tocopherol was the major isoform. Whole flours showed higher antioxidant properties. According to the obtained results, it is possible to allege all approved health claims referred to wheat, since all analyzed samples, especially whole flour and bran fraction, showed potential health benefits, as functional ingredients or functional foods, related with their phytochemical composition.This research was funded by Spanish Ministry of Science and Technology (project reference AGL2012-38345), the, ALIMNOVA research group (UCM 252/2017); the Foundation for Science and Technology (FCT, Portugal) and FEDER under Program PT2020 for financial support to CIMO (UID/AGR/00690/2013), A. Fernandes grant (SFRH/BPD/114753/2016), and L. Barros contract.info:eu-repo/semantics/publishedVersio

Bioactivity and chemical characterization in hydrophilic and lipophilic compounds of Chenopodium ambrosioides L

The bioactive properties (antioxidant and antitumour activities, and hepatotoxicity) of the infusion and methanolic extracts of Chenopodium ambrosioides L., a plant commonly used in Portuguese folk medicine, were compared. The chemical composition in hydrophilic (sugars, organic acids and phenolic compounds) and lipophilic (fatty acids and tocopherols) fractions were determined. In general, the infusion revealed higher antioxidant activity, while the methanolic extract was the only one showing antitumour effects against colon, cervical and hepatocellular carcinoma cell lines. No toxicity in non-tumour cells was observed either for the infusion or the extract. The studied plant proved to be a good source of natural antioxidants and other bioactive compounds, which may have industrial use. As far as we know, this is the first detailed chemical characterization and bioactivity evaluation of C. ambrosioides methanolic extract and infusion.The authors are grateful to Fundacao para a Ciencia e a Tecnologia (FCT, Portugal) for financial support to CIMO (strategic project PEst-OE/AGR/UI0690/2011). R.C. Calhelha and L. Barros also thank to FCT, POPH-QREN and FSE for their grants (SFRH/BPD/BPD/68344/2010 and SFRH/BPD/4609/2008, respectively). The GIP-USAL is financially supported by the Spanish Government through the Consolider-Ingenio 2010 Programme (FUN-C-FOOD, CSD2007-00063). M. Duenas thanks to the Programa Ramon y Cajal for a contract

Asthma and mental health among youth in high-risk service settings

Abstract Objective: To investigate the prevalence of asthma and mental health problems among representative samples of youth in high-risk service settings and the community, and to examine the relationship between asthma and mental health in these groups. Methods: Data were drawn from the Alternative Service Use Patterns of Youth with Serious Emotional Disturbance Study (SED) (n ¼ 1181), a combined representative, cross-sectional sample of youth in various clinical settings and the community. Multiple logistic regression analyses were used to examine the association between asthma and mental disorders. Demographic characteristics were investigated as potential confounders. Results: Asthma was common among 15.2% of youth in service settings and 18.8% of youth in the community. The prevalence of mental disorders was extremely high among youth with and without asthma in all service settings, and asthma was associated with increased prevalence of mental disorders among youth in the community, but not among youth in service settings. The relationship between asthma and internalizing disorders among youth in the community does not appear entirely attributable to confounding by demographics. Conclusions: Findings are consistent with and extend previous data by showing that both asthma and mental disorders are disproportionately common among youth in high-risk service settings. Almost half of youth with asthma in service settings meet diagnostic criteria for a mental disorder. Clinicians and policy makers who are responsible for the health care of youth in these high-risk groups should be aware that asthma is common, and that the prevalence of internalizing disorders are especially common among those with asthma

Lymphatic mimicry in maternal endothelial cells promotes placental spiral artery remodeling

Molecular heterogeneity of endothelial cells underlies their highly-specialized functions during changing physiological conditions within diverse vascular beds. For example, placental spiral arteries (SAs) undergo remarkable remodeling to meet the ever-growing demands of the fetus-a process which is deficient in preeclampsia. The extent to which maternal endothelial cells coordinate with immune cells and pregnancy hormones to promote SA remodeling remains largely unknown. Here we found that remodeled SAs expressed the lymphatic markers PROX1, LYVE1, and VEGFR3, mimicking lymphatic identity. Uterine natural killer (uNK) cells, which are required for SA remodeling and secrete VEGFC, were both sufficient and necessary for VEGFR3 activation in vitro and in mice lacking uNK cells, respectively. Using Flt4Chy/+ mice with kinase inactive VEGFR3 and Vegfcfl/fl;Vav1-Cre mice, we demonstrated that SA remodeling required VEGFR3 signaling, and that disrupted maternal VEGFR3 signaling contributed to late-gestation fetal growth restriction. Collectively, we identified a novel instance of lymphatic mimicry by which maternal endothelial cells promote SA remodeling, furthering our understanding of the vascular heterogeneity employed for the mitigation of pregnancy complications such as fetal growth restriction and preeclampsia