Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion. Electronic excitation, ligand loss from the metal ...centre, or a combination of both, creates changes in charge and spin density at the metal site that need to be controlled to optimize complexes for photocatalytic hydrogen production and selective carbon-hydrogen bond activation. An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)5 in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)4 species, a homogeneous catalyst with an electron deficiency at the Fe centre, in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)5 (refs 4, 16 - 20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.
Humpback whales (Megaptera novaeangliae) are a cosmopolitan species and perform long annual migrations between low-latitude breeding areas and high-latitude feeding areas. Their breeding populations ...appear to be spatially and genetically segregated due to long-term, maternally inherited fidelity to natal breeding areas. In the Southern Hemisphere, some humpback whale breeding populations mix in Southern Ocean waters in summer, but very little movement between Pacific and Atlantic waters has been identified to date, suggesting these waters constituted an oceanic boundary between genetically distinct populations. Here, we present new evidence of summer co-occurrence in the West Antarctic Peninsula feeding area of two recovering humpback whale breeding populations from the Atlantic (Brazil) and Pacific (Central and South America). As humpback whale populations recover, observations like this point to the need to revise our perceptions of boundaries between stocks, particularly on high latitude feeding grounds. We suggest that this "Southern Ocean Exchange" may become more frequent as populations recover from commercial whaling and climate change modifies environmental dynamics and humpback whale prey availability.
We utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal ...carbonyl photocatalyst Fe(CO)5 in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)4 which are observed following a charge transfer photoexcitation of Fe(CO)5 as reported in our previous study Wernet et al., Nature 520, 78 (2015). We find that branching of the reaction pathway likely happens in the 1A1 state of Fe(CO)4. A sub-picosecond time constant of the spin crossover from 1B2 to 3B2 is rationalized by the proposed 1B2 → 1A1 → 3B2 mechanism. Ultrafast ligation of the 1B2 Fe(CO)4 state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the 3B2 Fe(CO)4 ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via 1B2 → 1A1 → 1A′ Fe(CO)4EtOH pathway and the time scale of the 1A1 Fe(CO)4 state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.
Objective
Evidence on the impact of leisure time physical activity (LTPA) in pregnancy on birth size is inconsistent. We aimed to examine the association between LTPA during early and late pregnancy ...and newborn anthropometric outcomes.
Design
Individual level meta‐analysis, which reduces heterogeneity across studies.
Setting
A consortium of eight population‐based studies (seven European and one US) comprising 72 694 participants.
Methods
Generalised linear models with consistent inclusion of confounders (gestational age, sex, parity, maternal age, education, ethnicity, BMI, smoking, and alcohol intake) were used to test associations between self‐reported LTPA at either early (8–18 weeks gestation) or late pregnancy (30+ weeks) and the outcomes. Results were pooled using random effects meta‐analyses.
Main outcome measures
Birth weight, large‐for‐gestational age (LGA), macrosomia, small‐for‐gestational age (SGA), % body fat, and ponderal index at birth.
Results
Late, but not early, gestation maternal moderate to vigorous physical activity (MVPA), vigorous activity, and LTPA energy expenditure were modestly inversely associated with BW, LGA, macrosomia, and ponderal index, without heterogeneity (all: I2 = 0%). For each extra hour/week of MVPA, RR for LGA and macrosomia were 0.97 (95% CI: 0.96, 0.98) and 0.96 (95% CI: 0.94, 0.98), respectively. Associations were only modestly reduced after additional adjustments for maternal BMI and gestational diabetes. No measure of LTPA was associated with risk for SGA.
Conclusions
Physical activity in late, but not early, pregnancy is consistently associated with modestly lower risk of LGA and macrosomia, but not SGA.
Tweetable
In an individual participant meta‐analysis, late pregnancy moderate to vigorous physical activity modestly reduced birth size outcomes.
Tweetable
In an individual participant meta‐analysis, late pregnancy moderate to vigorous physical activity modestly reduced birth size outcomes.
Abstract
The structural and magnetic properties of seven CeMn
2
Ge
2-x
Si
x
compounds with x = 0.0–2.0 have been investigated in detail. Substitution of Ge with Si leads to a monotonic decrease of ...both a and c along with concomitant contraction of the unit cell volume and significant modifications of the magnetic states - a crossover from ferromagnetism at room temperature for Ge-rich compounds to antiferromagnetism for Si-rich compounds. The magnetic phase diagram has been constructed over the full range of CeMn
2
Ge
2-x
Si
x
compositions and co-existence of ferromagnetism and antiferromagnetism has been observed in CeMn
2
Ge
1.2
Si
0.8
, CeMn
2
Ge
1.0
Si
1.0
and CeMn
2
Ge
0.8
Si
1.2
with novel insight provided by high resolution neutron and X-ray synchrotron radiation studies. CeMn
2
Ge
2-x
Si
x
compounds (x = 0, 0.4 and 0.8) exhibit moderate isothermal magnetic entropy accompanied with a second-order phase transition around room temperature. Analysis of critical behaviour in the vicinity of T
C
inter
for CeMn
2
Ge
2
compound indicates behaviour consistent with three-dimensional Heisenberg model predictions.
We report the dramatic effect of applied pressure and magnetic field on the layered intermetallic compound Pr(0.5)Y(0.5)Mn(2)Ge(2). In the absence of pressure or magnetic field this compound displays ...interplanar ferromagnetism at room temperature and undergoes an isostructural first order magnetic transition (FOMT) to an antiferromagnetic state below 158 K, followed by another FOMT at 50 K due to the reemergence of ferromagnetism as praseodymium orders (T(C)(Pr)). The application of a magnetic field drives these two transitions towards each other, whereas the application of pressure drives them apart. Pressure also produces a giant magnetocaloric effect such that a threefold increase of the entropy change associated with the lower FOMT (at T(C)(Pr)) is seen under a pressure of 7.5 kbar. First principles calculations, using density functional theory, show that this remarkable magnetic behavior derives from the strong magnetoelastic coupling of the manganese layers in this compound.
High-resolution mapping of tropical forest carbon stocks can assist forest management and improve implementation of large-scale carbon retention and enhancement programs. Previous high-resolution ...approaches have relied on field plot and/or light detection and ranging (LiDAR) samples of aboveground carbon density, which are typically upscaled to larger geographic areas using stratification maps. Such efforts often rely on detailed vegetation maps to stratify the region for sampling, but existing tropical forest maps are often too coarse and field plots too sparse for high-resolution carbon assessments. We developed a top-down approach for high-resolution carbon mapping in a 16.5 million ha region (> 40%) of the Colombian Amazon - a remote landscape seldom documented. We report on three advances for large-scale carbon mapping: (i) employing a universal approach to airborne LiDAR-calibration with limited field data; (ii) quantifying environmental controls over carbon densities; and (iii) developing stratification- and regression-based approaches for scaling up to regions outside of LiDAR coverage. We found that carbon stocks are predicted by a combination of satellite-derived elevation, fractional canopy cover and terrain ruggedness, allowing upscaling of the LiDAR samples to the full 16.5 million ha region. LiDAR-derived carbon maps have 14% uncertainty at 1 ha resolution, and the regional map based on stratification has 28% uncertainty in any given hectare. High-resolution approaches with quantifiable pixel-scale uncertainties will provide the most confidence for monitoring changes in tropical forest carbon stocks. Improved confidence will allow resource managers and decision makers to more rapidly and effectively implement actions that better conserve and utilize forests in tropical regions.
Solanum sisymbriifolium Lam., is used in Paraguayan folk medicine claiming antihypertensive and diuretic properties.
This study aimed to determine the influence of chronic oral administration of the ...crude root extract and saponins obtained from S. sisymbriifolium Lam., on the blood pressure of male and female rats with hypertension induced by L-NAME, and its consequences on diuresis, the body weight, blood glucose, and level of serum parameters of liver and kidney functionality.
Wistar rats were randomly divided into seven male, and seven female groups (8 animals each), which received as 6-week pretreatment, 0.9% saline solution (two groups; 0.1mL/10 g of b.w.), L-arginine (100.0 mg/kg/day), enalapril (15.0 mg/kg/day), crude extract (CESs 100.0 mg/kg/day), and saponin purified fraction (1.0, and 10.0 mg/kg/day), and treated with L-NAME (20 mg/kg/day/i.p.) twice, 1, and 6 h after pre-treatment. The animals' body weight, glycemia, and blood pressure were recorded weekly, while serum, hepatic, renal, and histological parameters were analyzed at the end of 6-week of treatment.
A protective effect of CESs (100.0 mg/kg/day), and saponins (1.0, and 10.0 mg/kg/day) against hypertension induced by L-NAME was verified in the systolic, diastolic, and mean blood pressure values, which were significantly lower than the positive L-NAME-hypertensive control group (male and female) at the end of the 6-week treatment. Also, pretreatment with enalapril (15.0 mg/kg/day) induced an efficient protective activity, which validates the method used. Likewise, the volume of urine, creatinine, uric acid, urea, and electrolyte excretion was enhanced at the end of 6-week of treatment in concordance with the reduction in serum level of the same parameters, compatible with the improvement of the diuretic activity. The glycemia, body weight, heart rate, and functional hepato-renal parameters were not modified after a 6-week of treatment, in comparison to the control group, indicating relatively acceptable harmless properties of CESs and saponins. Interestingly, the HDL level in females was increased in contrast to male rats by chronic saponins treatment when compared with the negative control group.
It can be concluded that either the increment in blood pressure (systolic, diastolic, and median) or cardiorenal remodeling effects in male and female rats submitted to L-NAME-induced hypertensive condition, were prevented and well-preserved without a significant variation during a period of 6-week of pretreatment with CESs and saponins pretreatments. Likewise, an important diuretic effect was revealed after this period of treatment.
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Sedentary behaviour (SB) has emerged as a potential risk factor for metabolic health in youth. Knowledge on the determinants of SB in youth is necessary to inform future intervention development to ...reduce SB. A systematic review was conducted to identify predictors and determinants of SB in youth. Pubmed, Embase, CINAHL, PsycINFO and Web of Science were searched, limiting to articles in English, published between January 2000 and May 2014. The search strategy was based on four key elements and their synonyms: (a) sedentary behaviour, (b) determinants, (c) types of sedentary behaviours, (d) types of determinants. The full protocol is available from PROSPERO (PROSPERO 2014:CRD42014009823). Cross-sectional studies were excluded. The analysis was guided by the socio-ecological model. 37 studies were selected out of 2654 identified papers from the systematic literature search. Most studies were conducted in Europe (n = 13), USA (n = 11), and Australia (n = 10). The study quality, using the Qualsyst tool, was high with a median of 82 % (IQR: 74–91 %). Multiple potential determinants were studied in only one or two studies. Determinants were found at the individual, interpersonal, environmental and policy level but few studies examined a comprehensive set of factors at different levels of influences. Evidence was found for age being positively associated with total SB, and weight status and baseline assessment of screen time being positively associated with screen time (at follow-up). A higher playground density and a higher availability of play and sports equipment at school were consistently related to an increased total SB, although these consistent findings come from single studies. Evidence was also reported for the presence of safe places to cross roads and lengthening morning and lunch breaks being associated with less total SB. Future interventions to decrease SB levels should especially target children with overweight or obesity and should start at a young age. However, since the relationship of many determinants with SB remains inconsistent, there is still a need for more longitudinal research on determinants of SB in youth.
The current paradigm is that fibrosis promotes electrophysiological disorders and drives atrial fibrillation (AF). In this current study, we investigated the relation between the degree of fibrosis ...in human atrial tissue samples of controls and patients in various stages of AF and the degree of electrophysiological abnormalities.
The degree of fibrosis was measured in the atrial tissue and serum of patients in various stages of AF and the controls. Hereto, picrosirius and H&E staining were performed to quantify degree of total, endo-perimysial fibrosis, and cardiomyocyte diameter. Western blot quantified fibrosis markers: neural cell adhesion molecule, tissue inhibitor of metalloproteinase, lysyl oxidase, and α-smooth muscle actin. In serum, the ratio carboxyl-terminal telopeptide of collagen/matrix-metalloproteinase1 was determined. High-resolution epicardial mapping evaluated low-voltage areas and conduction abnormalities.
No significant differences were observed in the degree of fibrosis between the groups. Finally, no significant correlation-absolute nor spatial-was observed between all electrophysiological parameters and histological fibrosis markers.
No differences in the degree of fibrosis were observed in patients from various stages of AF compared to the controls. Moreover, electrophysiological abnormalities did not correlate with any of the fibrosis markers. The findings indicate that fibrosis is not the hallmark of structural remodeling in AF.
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