No abstract

We have prepared a series of 94.5%-enriched 57 Fe(II) complexes of tetramesitylporphyrin and octaethylporphyrin having various bis-or mixed axial ligation and investigated them by both NMR and Mo ¨ssbauer spectroscopy. The results obtained, and literature values for MbCO and cytochrome c, show a rough correlation between ∆E Q and δ Fe . This correlation suggested that the previously-reported chemical shifts of the complexes [TPPFeL 2 ], L ) pyridine-d 5 , and pyrrolidine (Nozawa, T.; Sato, M.; Hatano, M.; Kobayashi, N.; Osa, T. Chem. Lett. 1983, 1289) might be incorrect; we have thus used the rapid pulsing method of Schwenck to detect the signal of the bis-pyridine-d 5 complex at 11 715 ppm, within its predicted chemical shift range, based upon the δ Fe Vs ∆E Q correlation, and ∼4,400 ppm to lower shielding than originally reported. These findings emphasize the value of the Mo ¨ssbauer-NMR correlation in aiding the detection of 57 Fe NMR signals, as well as the perils of seeking these easily "folded" signals without such a correlation.

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The environment may lead to lower body mass index (BMI) and obesity risk by providing opportunities to be physically active. However, while intuitively appealing, associations are often inconsistent in direction and small scale. This longitudinal study examined if change in BMI and obesity was associated with the availability of physical activity (PA) facilities and parks and explored if these associations differed by age. Longitudinal data (n = 8,864, aged 18-86 years) were provided at baseline (wave I: 2010-2012) and follow up (wave II: 2013-2015) of the Yorkshire Health Study. BMI was calculated using self-reported height (cm) and weight (kg) (obesity = BMI≥30.00). To define availability, home addresses were geocoded based on postcode zone centroids and neighbourhood was defined as a 2 km radial buffer. PA facilities were sourced from Ordnance Survey Points of Interest (PoI) and parks were sourced from OpenStreetMap. Environmental data temporally matched individual-level baseline data collection. PA facilities (b = -0.006 [-0.015, 0.003]) and parks (b = -0.001 [-0.015, 0.013]) at baseline were not associated with change in BMI. Change in obesity was unrelated to parks (OR = 0.994 [0.975, 1.015]) and while PA facilities were related (OR = 0.979 [0.965, 0.993]), effects were small. A combined measure of the recreational PA environment including parks and PA facilities was unrelated to change in BMI and obesity. Despite this, statistically significant interactions were found for both PA facilities, parks, and change in obesity by age. Based on the premise that an individual's mobility varies with age, and although effects were small, this offers tentative evidence which suggests it may be useful for policymakers in Public Health and Planning to consider the impact of environmental interventions across the life course.