Subcomponent Exchange Transforms an Fe(II)4L4 Cage from High- to Low-Spin, Switching Guest Release in a Two-Cage System

Subcomponent exchange transformed new high-spin Fe(II)4L4 cage 1 into previously-reported low-spin Fe(II)4L4 cage 2: 2-formyl-6-methylpyridine was ejected in favor of the less sterically hindered 2-formylpyridine, with concomitant high- to low-spin transition of the cage's Fe(II) centers. High-spin 1 also reacted more readily with electron-rich anilines than 2, enabling the design of a system consisting of two cages that could release their guests in response to combinations of different stimuli. The addition of p-anisidine to a mixture of high-spin 1 and previously-reported low-spin Fe(II)4L6 cage 3 resulted in the destruction of 1 and the release of its guest. However, initial addition of 2-formylpyridine to an identical mixture of 1 and 3 resulted in the transformation of 1 into 2; added p-anisidine then reacted preferentially with 3 releasing its guest. The addition of 2-formylpyridine thus modulated the system's behavior, fundamentally altering its response to the subsequent signal p-anisidine.This work was funded by the European Research Council (695009) and EPSRC (EP/M01083X/1

An Area‐Specific, International Community‐Led Approach to Understanding and Addressing Equality, Diversity, and Inclusion Issues within Supramolecular Chemistry

Diversity, equality, and inclusion (DEI/EDI) are pressing issues in chemistry and the natural sciences. In this Essay we share how an area‐specific approach is “calling in” the community so that it can act to address EDI issues, and support those who are marginalised. Women In Supramolecular Chemistry (WISC) is an international network that aims to support equality, diversity, and inclusion within supramolecular chemistry. WISC has taken a field‐specific approach using qualitative research methods with scientists to identify the support that is needed and the problems the supramolecular community needs to address. Herein, we present survey data from the community which highlight the barriers that are faced by those who take career breaks for any reason, a common example is maternity leave, and the importance of mentoring to aid progression post‐PhD. In conclusion, we set out an interdisciplinary and creative approach to addressing EDI issues within supramolecular chemistry

Novel survey method finds dramatic decline of wild cotton-top tamarin population

For conservation purposes, accurate methods are required to track cotton-top tamarins in their natural habitat. As existing census methods are not appropriate for surveying these monkeys, a lure-transect method combined with playback vocalization was used here to allow accurate counting of the animals

Inspiratory muscle warm-up does not improve cycling time-trial performance

Purpose: This study examined the effects of an active cycling warm-up, with and without the addition of an inspiratory muscle warm-up (IMW), on 10-km cycling time-trial performance

Improved estimates of preindustrial biomass burning reduce the magnitude of aerosol climate forcing in the Southern Hemisphere.

Fire plays a pivotal role in shaping terrestrial ecosystems and the chemical composition of the atmosphere and thus influences Earth's climate. The trend and magnitude of fire activity over the past few centuries are controversial, which hinders understanding of preindustrial to present-day aerosol radiative forcing. Here, we present evidence from records of 14 Antarctic ice cores and 1 central Andean ice core, suggesting that historical fire activity in the Southern Hemisphere (SH) exceeded present-day levels. To understand this observation, we use a global fire model to show that overall SH fire emissions could have declined by 30% over the 20th century, possibly because of the rapid expansion of land use for agriculture and animal production in middle to high latitudes. Radiative forcing calculations suggest that the decreasing trend in SH fire emissions over the past century largely compensates for the cooling effect of increasing aerosols from fossil fuel and biofuel sources

Improved estimates of preindustrial biomass burning reduce the magnitude of aerosol climate forcing in the Southern Hemisphere.

Fire plays a pivotal role in shaping terrestrial ecosystems and the chemical composition of the atmosphere and thus influences Earth's climate. The trend and magnitude of fire activity over the past few centuries are controversial, which hinders understanding of preindustrial to present-day aerosol radiative forcing. Here, we present evidence from records of 14 Antarctic ice cores and 1 central Andean ice core, suggesting that historical fire activity in the Southern Hemisphere (SH) exceeded present-day levels. To understand this observation, we use a global fire model to show that overall SH fire emissions could have declined by 30% over the 20th century, possibly because of the rapid expansion of land use for agriculture and animal production in middle to high latitudes. Radiative forcing calculations suggest that the decreasing trend in SH fire emissions over the past century largely compensates for the cooling effect of increasing aerosols from fossil fuel and biofuel sources

Synchrotron tomography of intervertebral disc deformation quantified by digital volume correlation reveals microstructural influence on strain patterns

The intervertebral disc (IVD) has a complex and multiscale extracellular matrix structure which provides unique mechanical properties to withstand physiological loading. Low back pain has been linked to degeneration of the disc but reparative treatments are not currently available. Characterising the disc’s 3D microstructure and its response in a physiologically relevant loading environment is required to improve understanding of degeneration and to develop new reparative treatments. In this study, techniques for imaging the native IVD, measuring internal deformation and mapping volumetric strain were applied to an in situ compressed ex vivo rat lumbar spine segment. Synchrotron X-ray micro-tomography (synchrotron CT) was used to resolve IVD structures at microscale resolution. These image data enabled 3D quantification of collagen bundle orientation and measurement of local displacement in the annulus fibrosus between sequential scans using digital volume correlation (DVC). The volumetric strain mapped from synchrotron CT provided a detailed insight into the micromechanics of native IVD tissue. The DVC findings showed that there was no slipping at lamella boundaries, and local strain patterns were of a similar distribution to the previously reported elastic network with some heterogeneous areas and maximum strain direction aligned with bundle orientation, suggesting bundle stretching and sliding. This method has the potential to bridge the gap between measures of macro-mechanical properties and the local 3D micro-mechanical environment experienced by cells. This is the first evaluation of strain at the micro scale level in the intact IVD and provides a quantitative framework for future IVD degeneration mechanics studies and testing of tissue engineered IVD replacements

Spatial Variation in Foraging Behaviour of a Marine Top Predator (Phoca vitulina) Determined by a Large-Scale Satellite Tagging Program

The harbour seal (Phoca vitulina) is a widespread marine predator in Northern Hemisphere waters. British populations have been subject to rapid declines in recent years. Food supply or inter-specific competition may be implicated but basic ecological data are lacking and there are few studies of harbour seal foraging distribution and habits. In this study, satellite tagging conducted at the major seal haul outs around the British Isles showed both that seal movements were highly variable among individuals and that foraging strategy appears to be specialized within particular regions. We investigated whether these apparent differences could be explained by individual level factors: by modelling measures of trip duration and distance travelled as a function of size, sex and body condition. However, these were not found to be good predictors of foraging trip duration or distance, which instead was best predicted by tagging region, time of year and inter-trip duration. Therefore, we propose that local habitat conditions and the constraints they impose are the major determinants of foraging movements. Specifically the distance to profitable feeding grounds from suitable haul-out locations may dictate foraging strategy and behaviour. Accounting for proximity to productive foraging resources is likely to be an important component of understanding population processes. Despite more extensive offshore movements than expected, there was also marked fidelity to the local haul-out region with limited connectivity between study regions. These empirical observations of regional exchange at short time scales demonstrates the value of large scale electronic tagging programs for robust characterization of at-sea foraging behaviour at a wide spatial scale