Electron-Transfer Chemistry of Ru−Linker−(Heme)-Modified Myoglobin: Rapid Intraprotein Reduction of a Photogenerated Porphyrin Cation Radical

We report the synthesis and characterization of RuC7, a complex in which a heme is covalently attached to a [Ru(bpy)_3]^(2+) complex through a −(CH_2)_7− linker. Insertion of RuC7 into horse heart apomyoglobin gives RuC7Mb, a Ru(heme)−protein conjugate in which [Ru(bpy)_3]^(2+) emission is highly quenched. The rate of photoinduced electron transfer (ET) from the resting (Ru^(2+)/Fe^(3+)) to the transient (Ru^(3+)/Fe^(2+)) state of RuC7Mb is >10^8 s^(-1); the back ET rate (to regenerate Ru^(2+)/Fe^(3+)) is 1.4 × 10^7 s^(-1). Irreversible oxidative quenching by [Co(NH_3)_5Cl]^(2+) generates Ru^(3+)/Fe^(3+):  the Ru^(3+) complex then oxidizes the porphyrin to a cation radical (P^(•+)); in a subsequent step, P^(•+) oxidizes both Fe^(3+) (to give Fe^(IV)═O) and an amino acid residue. The rate of intramolecular reduction of P^(•+) is 9.8 × 10^3 s^(-1); the rate of ferryl formation is 2.9 × 10^3 s^(-1). Strong EPR signals attributable to tyrosine and tryptophan radicals were recorded after RuC7MbM^(3+) (M = Fe, Mn) was flash-quenched/frozen

Substrate-Selective Adhesion of Metal Nanoparticles to Graphene Devices

Nanostructured electronic devices, such as those based on graphene, are typically grown on top of the insulator SiO2. Their exposure to a flux of small size-selected silver nanoparticles has revealed remarkably selective adhesion: the graphene channel can be made fully metallized while the insulating substrate remains coverage-free. This conspicuous contrast derives from the low binding energy between the metal nanoparticles and a contaminant-free passivated silica surface. In addition to providing physical insight into nanoparticle adhesion, this effect may be of value in applications involving deposition of metallic layers on device working surfaces: it eliminates the need for masking the insulating region and the associated extensive and potentially deleterious pre- and postprocessing.Comment: 29 page

Effect of finishing diet and duration on the sensory quality and volatile profile of lamb meat

peer-reviewedAnimal production factors can affect the sensory quality of lamb meat. The study investigated the effect of diet composition and duration of consumption on the proximate analysis, volatile profile and sensory quality of lamb meat. Ninety-nine male Texel × Scottish Blackface lambs were raised at pasture for 10 months before being assigned in groups of 11 to one of the following treatments: 100% Silage (S) for 36 (S36), 54 (S54) or 72 (S72) days; 50% Silage - 50% Concentrate (SC) for 36 (SC36), 54 (SC54) or 72 (SC72) days; 100% Concentrate (C) for 36 (C36) or 54 (C54) or 72 (C72) days. A trained sensory panel found Intensity of Lamb Aroma, Dry Aftertaste and Astringent Aftertaste to be higher in meat from lambs on the concentrate diet. Discriminant analysis showed that the volatile profile enabled discrimination of lamb based on dietary treatment but the volatile differences were insufficient to impact highly on sensory quality. Muscle from animals in the S54 group had higher Manure/Faecal Aroma and Woolly Aroma than the SC54 and C54 groups, possibly related to higher levels of indole and skatole. Further research is required to establish if these small differences would influence consumer acceptability.The financial support of the Irish Department of Agriculture, Food and the Marine (project 11/SF/310) and of the Teagasc Walsh Fellowship Programme (award 2013058) is gratefully acknowledged

Raptor Interactions with Wind Energy: Case Studies from Around the World

The global potential for wind power generation is vast, and the number of installations is increasing rapidly. We review case studies from around the world of the effects on raptors of wind-energy development. Collision mortality, displacement, and habitat loss have the potential to cause population-level effects, especially for species that are rare or endangered. The impact on raptors has much to do with their behavior, so careful siting of wind-energy developments to avoid areas suited to raptor breeding, foraging, or migration would reduce these effects. At established wind farms that already conflict with raptors, reduction of fatalities may be feasible by curtailment of turbines as raptors approach, and offset through mitigation of other human causes of mortality such as electrocution and poisoning, provided the relative effects can be quantified. Measurement of raptor mortality at wind farms is the subject of intense effort and study, especially where mitigation is required by law, with novel statistical approaches recently made available to improve the notoriously difficult-to-estimate mortality rates of rare and hard-to-detect species. Global standards for wind farm placement, monitoring, and effects mitigation would be a valuable contribution to raptor conservation worldwide.publishedVersio

The effects of nitroxyl (HNO) on soluble guanylate cyclase activity: interactions at ferrous heme and cysteine thiols

It has been previously proposed that nitric oxide (NO) is the only biologically relevant nitrogen oxide capable of activating the enzyme soluble guanylate cyclase (sGC). However, recent reports implicate HNO as another possible activator of sGC. Herein, we examine the affect of HNO donors on the activity of purified bovine lung sGC and find that, indeed, HNO is capable of activating this enzyme. Like NO, HNO activation appears to occur via interaction with the regulatory ferrous heme on sGC. Somewhat unexpectedly, HNO does not activate the ferric form of the enzyme. Finally, HNO-mediated cysteine thiol modification appears to also affect enzyme activity leading to inhibition. Thus, sGC activity can be regulated by HNO via interactions at both the regulatory heme and cysteine thiols

The importance of both setting and intensity of physical activity in relation to non-clinical anxiety and depression

Physical activity is associated with good physical and mental health. Current recommendations suggest that people should achieve 30 minutes of moderate-intensity activity most days of the week to gain health benefits. This activity may be accumulated in leisure time, in active commuting, at work or in the home. Here we look at the cross-sectional relationship between physical activity and mental health as measured by the HADS anxiety and depression scores in a sample of 1,742 participants from a Scottish general population survey. The participants were men and women in three age cohorts aged around 24, 44 and 64 years who, in 1995, were interviewed face to face and also self-completed the HADS depression and anxiety scale. Respondents reported their levels of physical activity at work, in the home and in leisure time; the intensities of activity were also determined. Physical activity was related to depression scores but not to anxiety scores. There was no relationship between work physical activity and depression score. Among women, depression score increased with each additional episode of vigorous home activity. In both sexes, depression score decreased with each additional episode of vigorous leisure activity, but among men the decrease in depression score with moderate leisure activity was reversed if a lot of moderate activity was undertaken. We have found a variable relationship between depression scores and various settings for physical activity. Researchers, policymakers and practitioners who are interested in the relationship between physical activity and mental health should take into account the setting for activity as well as frequency, duration and intensity of activity

A Family of Water Immiscible, Dipolar Aprotic, Diamide Solvents from Succinic Acid

Three dipolar aprotic solvents were designed to possess high dipolarity and low toxicity: N , N , N ', N '-tetrabutylsuccindiamide (TBSA), N , N '-diethyl- N , N '-dibutylsuccindiamide (EBSA), N , N '-dimethyl- N , N '-dibutylsuccindiamide (MBSA). They were synthesized catalytically using a K60 silica catalyst in a solventless system. Their water-immiscibility stands out as an unusual and useful property for dipolar aprotic solvents. They were tested in a model Heck reaction, metal-organic framework syntheses, and a selection of polymer solubility experiments where their performances were found to be comparable to traditional solvents. Furthermore, MBSA was found to be suitable for the production of an industrially-relevant membrane from polyethersulphone. An integrated approach involving in silico analysis based on available experimental information, prediction model outcomes and read across data, as well as a panel of in vitro reporter gene assays covering a broad range of toxicological endpoints was used to assess toxicity. These in silico and in vitro tests suggested no alarming indications of toxicity in the new solvents

Assessment of C, N, and Si Isotopes as Tracers of Past Ocean Nutrient and Carbon Cycling

28 pages, 6 figures, 1 box, 1 appendix.-- Data Availability Statement: Data sets presented in this research are available via the following repositories and study (listed by Figure): Figures 3 and 4: (1)δ13CDIC:(a) CLIVAR P16S (Feely et al., 2008) from GLODAPv2.2020 database (Olsen et al., 2020): https://www.glodap.info/index.php/merged-and-adjusted-data-product/. (b) GEOTRACES GA03 (Quay & Wu, 2015) and GP16 (P. Quay, unpublished data) from GEOTRACES IDP2017 (Schlitzer et al., 2018): https://www.bodc.ac.uk/geotraces/data/idp2017/. (2) δ15Nnitrate:(a) CLIVAR P16S (Rafter et al., 2013) from BCO-DMO: https://www.bco-dmo.org/dataset/651722. (b) GEOTRACES GA03 (Marconi et al., 2015) and GP16 (Peters et al., 2018) from GEOTRACES IDP2017 (Schlitzer et al., 2018): https://www.bodc.ac.uk/geotraces/data/idp2017/. (3) δ30Si: GEOTRACES GA03 (Brzezinski & Jones, 2015) and GIPY04 (Fripiat et al., 2012) from GEOTRACES IDP2017 (Schlitzer et al., 2018): https://www.bodc.ac.uk/geotraces/data/idp2017/. (4) Figure 4a POC Flux (DeVries & Weber, 2017): SIMPLE-TRIM Output from https://tdevries.eri.ucsb.edu/models-and-data-products/. Figure 5: (a) Antarctic CO2 composite: https://www.ncdc.noaa.gov/paleo-search/study/17975. (b) ∆δ13Cthermocline-deep from Ziegler et al. (2013) supporting information: https://www.nature.com/articles/ngeo1782; ∆δ13Cepifaunal-infaunal (Hoogakker et al., 2018): https://doi.pangaea.de/10.1594/PANGAEA.891185. (c) SAZ FB-δ15N (Martínez-García et al., 2014): https://www.ncdc.noaa.gov/paleo/study/18318; AZ DB-δ15N (Studer et al., 2015): https://doi.pangaea.de/10.1594/PANGAEA.848271. (d) SAZ Fe flux (Martínez-García et al., 2014): https://www.ncdc.noaa.gov/paleo/study/18318. (e) AZ diatom δ30Si (Robinson et al., 2014): https:// www.ncdc.noaa.gov/paleo/study/17917. Figure 6: (a) and (b) Benthic foraminifera δ18O and δ13C (Zachos et al., 2001): https:// www.ncdc.noaa.gov/paleo/study/8674. (c) FB-δ15N from Kast et al. (2019) supporting information data: https://science.sciencemag.org/content/suppl/2019/04/24/364.6438.386.DC1. (d) and (e) Diatom, sponge, and radiolarian δ30Si in Egan et al. (2013) supporting information: https://www.sciencedirect.com/science/article/pii/S0012821X13002185, Fontorbe et al. (2016) supporting information: https://www.sciencedirect.com/science/article/pii/S0012821X16304265, and Fontorbe et al. (2017) supporting information: https://agupubs.onlinelibrary.wiley.com/doi/full/10.1002/2017PA003090Biological productivity in the ocean directly influences the partitioning of carbon between the atmosphere and ocean interior. Through this carbon cycle feedback, changing ocean productivity has long been hypothesized as a key pathway for modulating past atmospheric carbon dioxide levels and hence global climate. Because phytoplankton preferentially assimilate the light isotopes of carbon and the major nutrients nitrate and silicic acid, stable isotopes of carbon (C), nitrogen (N), and silicon (Si) in seawater and marine sediments can inform on ocean carbon and nutrient cycling, and by extension the relationship with biological productivity and global climate. Here, we compile water column C, N, and Si stable isotopes from GEOTRACES-era data in four key ocean regions to review geochemical proxies of oceanic carbon and nutrient cycling based on the C, N, and Si isotopic composition of marine sediments. External sources and sinks as well as internal cycling (including assimilation, particulate matter export, and regeneration) are discussed as likely drivers of observed C, N, and Si isotope distributions in the ocean. The potential for C, N, and Si isotope measurements in sedimentary archives to record aspects of past ocean C and nutrient cycling is evaluated, along with key uncertainties and limitations associated with each proxy. Constraints on ocean C and nutrient cycling during late Quaternary glacial-interglacial cycles and over the Cenozoic are examined. This review highlights opportunities for future research using multielement stable isotope proxy applications and emphasizes the importance of such applications to reconstructing past changes in the oceans and climate systemThis workshop was funded by the United States National Science Foundation (NSF) through the GEOTRACES program, the international Past Global Changes (PAGES) project, which in turn received support from the Swiss Academy of Sciences and NSF, and the French national program LEFE (Les Enveloppes Fluides et l'Environnement). [...] This study was supported by PAGES, LEFE, and GEOTRACES through NSF. J. R. Farmer acknowledges support from the Max Planck Society, the Tuttle Fund of the Department of Geosciences of Princeton University, the Grand Challenges Program of the Princeton Environmental Institute, and through Exxon Mobil via the Andlinger Center for Energy and the Environment of Princeton University. Open access funding enabled and organized by Projekt DEAL. [...] With the institutional support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S

Compartmentalisation and localisation of the translation initiation factor (eIF) 4F complex in normally growing fibroblasts

Previous observations of association of mRNAs and ribosomes with subcellular structures highlight the importance of localised translation. However, little is known regarding associations between eukaryotic translation initiation factors and cellular structures within the cytoplasm of normally growing cells. We have used detergent-based cellular fractionation coupled with immunofluorescence microscopy to investigate the subcellular localisation in NIH3T3 fibroblasts of the initiation factors involved in recruitment of mRNA for translation, focussing on eIF4E, the mRNA cap-binding protein, the scaffold protein eIF4GI and poly(A) binding protein (PABP). We find that these proteins exist mainly in a soluble cytosolic pool, with only a subfraction tightly associated with cellular structures. However, this "associated" fraction was enriched in active "eIF4F" complexes (eIF4E.eIF4G.eIF4A.PABP). Immunofluorescence analysis reveals both a diffuse and a perinuclear distribution of eIF4G, with the perinuclear staining pattern similar to that of the endoplasmic reticulum. eIF4E also shows both a diffuse staining pattern and a tighter perinuclear stain, partly coincident with vimentin intermediate filaments. All three proteins localise to the lamellipodia of migrating cells in close proximity to ribosomes, microtubules, microfilaments and focal adhesions, with eIF4G and eIF4E at the periphery showing a similar staining pattern to the focal adhesion protein vinculin