Understanding substrate substituent effects to improve catalytic efficiency in the SABRE hyperpolarisation process.

The use of parahydrogen based hyperpolarisation in NMR is becoming more widespread due to the rapidly expanding range of suitable target molecules and low-cost of parahydrogen production. Hyperpolarisation via SABRE catalysis employs a metal complex to transfer polarisation from parahydrogen into a substrate whilst they are bound. In this paper we present a quantitative study of substrate-iridium ligation effects by reference to the substrates 4-chloropyridine (A), 4-pyridinecarboxaldehyde methyl hemiacetal (B), 4-methylpyridine (C) and 4-methoxypyridine (D), and evaluate the role they play in the SABRE catalysis. Substrates whose substituents enable stronger associations yield slower substrate dissociation rates (k d). A series of variable temperature studies link these exchange rates to optimal SABRE performance and reveal the critical impact of NMR relaxation times (T 1). Longer catalyst residence times are shown to result in shorter substrate T 1 values in solution as binding to iridium promotes relaxation thereby not only reducing SABRE efficiency but decreasing the overall level of achieved hyperpolarisation. Based on these data, a route to achieve more optimal SABRE performance is defined.

Complementary landmarks facilitate ant navigation.

Visual landmarks are important navigational aids to many animals, and when more than one is available their juxtaposition can convey valuable new information to a navigator about progress toward a goal, depending on the landmarks' comparative distinctiveness. We investigated the effect of presenting rock ant colonies (Temnothorax albipennis) with identical horizontal landmarks either side of their route, versus one horizontal landmark paired with a sloping landmark, as they navigated to a new nest site. Our findings suggest that ants can obtain more navigational information from a combination of dissimilar landmarks: the average tortuosity of the route taken between old and new nests was significantly lower when a horizontal landmark was paired with a monotonically downward sloping landmark (the paths were more direct). The impact on available navigational information from the similarity or dissimilarity of nearby landmarks is likely made through more distinctive visual panoramas, and could be an influential factor in individual and collective animal decision-making about which routes are followed. Furthermore, the effect of landmark complementarity may be relevant to a wide range of species, including other insects or birds, and highlights the possibility that there is an intrinsic difference in the informational content of natural vs. artificial environments.