The frequency of osteogenic activities and the pattern of intermittence between periods of physical activity and sedentary behaviour affects bone mineral content: the cross-sectional NHANES study

BACKGROUND: Sedentary behaviours, defined as non exercising seated activities, have been shown to have deleterious effects on health. It has been hypothesised that too much sitting time can have a detrimental effect on bone health in youth. The aim of this study is to test this hypothesis by exploring the association between objectively measured volume and patterns of time spent in sedentary behaviours, time spent in specific screen-based sedentary pursuits and bone mineral content (BMC) accrual in youth. METHODS: NHANES 2005–2006 cycle data includes BMC of the femoral and spinal region via dual-energy X-ray absorptiometry (DEXA), assessment of physical activity and sedentary behaviour patterns through accelerometry, self reported time spent in screen based pursuits (watching TV and using a computer), and frequency of vigorous playtime and strengthening activities. Multiple regression analysis, stratified by gender was performed on N = 671 males and N = 677 females aged from 8 to 22 years. RESULTS: Time spent in screen-based sedentary behaviours is negatively associated with femoral BMC (males and females) and spinal BMC (females only) after correction for time spent in moderate and vigorous activity. Regression coefficients indicate that an additional hour per day of screen-based sitting corresponds to a difference of −0.77 g femoral BMC in females [95% CI: -1.31 to −0.22] and of −0.45 g femoral BMC in males [95% CI: -0.83 to −0.06]. This association is attenuated when self-reported engagement in regular (average 5 times per week) strengthening exercise (for males) and vigorous playing (for both males and females) is taken into account. Total sitting time and non screen-based sitting do not appear to have a negative association with BMC, whereas screen based sedentary time does. Patterns of intermittence between periods of sitting and moderate to vigorous activity appears to be positively associated with bone health when activity is clustered in time and inter-spaced with long continuous bouts of sitting. CONCLUSIONS: Some specific sedentary pursuits (screen-based) are negatively associated with bone health in youth. This association is specific to gender and anatomical area. This relationship between screen-based time and bone health is independent of the total amount of physical activity measured objectively, but not independent of self-reported frequency of strengthening and vigorous play activities. The data clearly suggests that the frequency, rather than the volume, of osteogenic activities is important in counteracting the effect of sedentary behaviour on bone health. The pattern of intermittence between sedentary periods and activity also plays a role in bone accrual, with clustered short bouts of activity interspaced with long periods of sedentary behaviours appearing to be more beneficial than activities more evenly spread in time

Universal DNA methylation age across mammalian tissues

Aging, often considered a result of random cellular damage, can be accurately estimated using DNA methylation profiles, the foundation of pan-tissue epigenetic clocks. Here, we demonstrate the development of universal pan-mammalian clocks, using 11,754 methylation arrays from our Mammalian Methylation Consortium, which encompass 59 tissue types across 185 mammalian species. These predictive models estimate mammalian tissue age with high accuracy (r > 0.96). Age deviations correlate with human mortality risk, mouse somatotropic axis mutations and caloric restriction. We identified specific cytosines with methylation levels that change with age across numerous species. These sites, highly enriched in polycomb repressive complex 2-binding locations, are near genes implicated in mammalian development, cancer, obesity and longevity. Our findings offer new evidence suggesting that aging is evolutionarily conserved and intertwined with developmental processes across all mammals

Counteranion-Dependent Reaction Pathways in the Protonation of Cationic Ruthenium−Vinylidene Complexes

The tetraphenylborate salts of the cationic vinylidene complexes [Cp*Ru=C=CHR(iPr2PNHPy)]+ (R = p-C6H4CF3 (1a-BPh4), Ph (1b-BPh4), p-C6H4CH3 (1c- BPh4), p-C6H4Br (1d-BPh4), tBu (1e-BPh4), H (1f-BPh4)) have been protonated using an excess of HBF4·OEt2 in CD2Cl2, furnishing the dicationic carbyne complexes [Cp*Ru≡CCH2R(iPr2PNHPy)]2+ (R = p-C6H4CF3 (2a), Ph (2b), p-C6H4CH3 (2c), p-C6H4Br (2d), tBu (2e), H (2f)), which were characterized in solution at low temperature by NMR spectroscopy. The corresponding reaction of the chloride salts 1a-Cl, 1b-Cl, 1c-Cl, and 1d-Cl followed a different pathway, instead affording the novel alkene complexes [Cp*RuCl(κ1(N),η2(C,C)-C5H4N-NHPiPr2CH=CHR)][BF4] (3a−d). In these species, the entering proton is located at the α- carbon atom of the former vinylidene ligand, which also forms a P−C bond with the phosphorus atom of the iPr2PNHPy ligand. To shed light on the reaction mechanism, DFT calculations have been performed by considering several protonation sites. The computational results suggest metal protonation followed by insertion. The coordination of chloride to ruthenium leads to alkenyl species which can undergo a P−C coupling to yield the corresponding alkene complexes. The noncoordinating nature of [BPh4]− does not allow the stabilization of the unsaturated species coming from the insertion step, thus preventing this alternative pathway

Syntheses and Electronic Properties of Rhodium(III) Complexes Bearing a Redox-Active Ligand

A series of rhodium(III) complexes of the redox-active ligand, H(L = bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amido), was prepared, and the electronic properties were studied. Thus, heating an ethanol solution of commercial RhCl3·3H2O with H(L) results in the precipitation of insoluble [H(L)]RhCl3, 1. The reaction of a methanol suspension of [H(L)]RhCl3 with NEt4OH causes ligand deprotonation and affords nearly quantitative yields of the soluble, deep-green, title compound (NEt4)[(L)RhCl3]·H2O, 2·H2O. Complex 2·H2O reacts readily with excess pyridine, triethylphosphine, or pyrazine (pyz) to eliminate NEt4Cl and give charge-neutral complexes trans-(L)RhCl2(py), trans-3, trans-(L)RhCl2(PEt3), trans- 4, or trans-(L)RhCl2(pyz), trans-5, where the incoming Lewis base is trans- to the amido nitrogen of the meridionally coordinating ligand. Heating solutions of complexes trans-3 or trans-4 above about 100 °C causes isomerization to the appropriate cis-3 or cis-4. Isomerization of trans-5 occurs at a much lower temperature due to pyrazine dissociation. Cis-3 and cis- 5 could be reconverted to their respective trans- isomers in solution at 35 °C by visible light irradiation. Complexes [(L)Rh(py)2Cl](PF6), 6, [(L)Rh(PPh3)(py)Cl](PF6), 7, [(L)Rh(PEt3)2Cl](PF6), 8, and [(L)RhCl(bipy)](OTf = triflate), 9, were prepared from 2·H2O by using thallium(I) salts as halide abstraction agents and excess Lewis base. It was not possible to prepare dicationic complexes with three unidentate pyridyl or triethylphosphine ligands; however, the reaction between 2, thallium(I) triflate, and the tridentate 4′-(4-methylphenyl)-2,2′:6′,2″-terpyridine (ttpy) afforded a high yield of [(L)Rh(ttpy)]- (OTf)2, 10. The solid state structures of nine new complexes were obtained. The electrochemistry of the various derivatives in CH2Cl2 showed a ligand-based oxidation wave whose potential depended mainly on the charge of the complex, and to a lesser extent on the nature and the geometry of the other supporting ligands. Thus, the oxidation wave for 2 with an anionic complex was found at +0.27 V versus Ag/AgCl in CH2Cl2, while those waves for the charge-neutral complexes 3−5 were found between +0.38 to +0.59 V, where the cis- isomers were about 100 mV more stable toward oxidation than the trans- isomers. The oxidation waves for 6−9 with monocationic complexes occurred in the range +0.74 to 0.81 V while that for 10 with a dicationic complex occurred at +0.91 V. Chemical oxidation of trans-3, cis-3, and 8 afforded crystals of the singly oxidized complexes, [trans- (L)RhCl2(py)](SbCl6), cis-[(L)RhCl2(py)](SbCl4)·2CH2Cl2, and [(L)Rh(PEt3)2Cl](SbCl6)2, respectively. Comparisons of structural and spectroscopic features combined with the results of density functional theory (DFT) calculations between nonoxidized and oxidized forms of the complexes are indicative of the ligand-centered radicals in the oxidized derivatives

Bridging the accessibility gap in Open Educational Resources

Open Educational Resources (OER) are being fostered as a global movement for providing educational opportunities to all. However, people with disabilities are still excluded from full participation because of the lack of accessibility of OER websites, as well as of the resources themselves. This work presents a proposal for the design of OER websites that would enable equitable access for all users. This design aims to bridge the accessibility gap through the personalization of the whole OER environment to facilitate an accessible User Experience (UX) based on a user profile that includes the self-identification of disability status. This profile configures not only the “look and feel” of the interface but also the delivery of educational resources suitable for this user profile. To achieve this purpose, the design goes beyond compliance with the ISO/IEC 40500 W3C Web Content Accessibility Guidelines (WCAG) 2.0, since it includes the personalization of the accessible experience through usability considerations and adaptations of educational resources. The delivery of educational resources matches the user’s profile with regard to their sensory abilities, cognitive faculties and their requirements of functionality control, display layout and language. As a proof of concept, we have developed an OER website based on this design and have conducted a set of UX tests that include users with different disabilities. The test results confirm the feasibility and suitability of our design regarding accessible UX. Finally, the contribution of this document arises from the explicit recognition of the particular needs associated with the disability profiles to establish the response of the entire OER system which enables a truly inclusive experience by exempting the user from performing configuration tasks

Universal DNA methylation age across mammalian tissues

Aging, often considered a result of random cellular damage, can be accurately estimated using DNA methylation profiles, the foundation of pan-tissue epigenetic clocks. Here, we demonstrate the development of universal pan-mammalian clocks, using 11,754 methylation arrays from our Mammalian Methylation Consortium, which encompass 59 tissue types across 185 mammalian species. These predictive models estimate mammalian tissue age with high accuracy (r > 0.96). Age deviations correlate with human mortality risk, mouse somatotropic axis mutations and caloric restriction. We identified specific cytosines with methylation levels that change with age across numerous species. These sites, highly enriched in polycomb repressive complex 2-binding locations, are near genes implicated in mammalian development, cancer, obesity and longevity. Our findings offer new evidence suggesting that aging is evolutionarily conserved and intertwined with developmental processes across all mammals.Publisher PDFPeer reviewe