Iron/N-doped graphene nano-structured catalysts for general cyclopropanation of olefins

The first examples of heterogeneous Fe-catalysed cyclopropanation reactions are presented. Pyrolysis of in situ-generated iron/phenanthroline complexes in the presence of a carbonaceous material leads to specific supported nanosized iron particles, which are effective catalysts for carbene transfer reactions. Using olefins as substrates, cyclopropanes are obtained in high yields and moderate diastereoselectivities. The developed protocol is scalable and the activity of the recycled catalyst after deactivation can be effectively restored using an oxidative reactivation protocol under mild conditions

Life in a Harsh Environment: The Effects of Age, Sex, Reproductive Condition, and Season on Hair Cortisol Concentration in a Wild Non-Human Primate

Hair cortisol concentration (HCC) provides a long-term retrospective measure of hypothalamic–pituitary–adrenal axis activity, and is increasingly used to assess the life history, health and ecology of wild mammals. Given that sex, age, season and pregnancy influence HCC, and that it may indicate ongoing stress, we examined HCC in common marmosets (Callithrix jacchus) naturally inhabiting a hot and dry semi-desert like habitat, Caatinga, in northeastern Brazil. We trapped, measured, weighed, marked and collected shaved hair from the back of the neck of 61 wild marmosets during the wet and dry seasons. Using enzyme immunoassay, we found that HCC was higher in the dry season compared with the wet season among all age/sex classes. Females had significantly higher HCC than males, juveniles had higher HCC than adults, and reproductively active adult females and non-pregnant/non lactating adult females did not differ in HCC. There were no interaction effects of sex, age, group, or season on HCC. The magnitude of the effect of this extremely hot and dry environment (average yearly rainfall was only 271 mm) on HCC in common marmosets is difficult to ascertain as these animals are also experiencing a variety of other stressors. However, the elevated HCC seen in common marmosets during the 5–8 month dry season, suggests these primates face an extended period of heat, water and possibly nutritional stress, which appears to result in a high rate of juvenile mortality

Entanglement of dark electron-nuclear spin defects in diamond

A promising approach for multi-qubit quantum registers is to use optically addressable spins to control multiple dark electron-spin defects in the environment. While recent experiments have observed signatures of coherent interactions with such dark spins, it is an open challenge to realize the individual control required for quantum information processing. Here we demonstrate the initialisation, control and entanglement of individual dark spins associated to multiple P1 centers, which are part of a spin bath surrounding a nitrogen-vacancy center in diamond. We realize projective measurements to prepare the multiple degrees of freedom of P1 centers - their Jahn-Teller axis, nuclear spin and charge state - and exploit these to selectively access multiple P1s in the bath. We develop control and single-shot readout of the nuclear and electron spin, and use this to demonstrate an entangled state of two P1 centers. These results provide a proof-of-principle towards using dark electron-nuclear spin defects as qubits for quantum sensing, computation and networks

Homeodomain Interacting Protein Kinase 2 Activation Compromises Endothelial Cell Response to Laminar Flow: Protective Role of p21waf1,cip1,sdi1

BACKGROUND: In the cardiovascular system, laminar shear stress (SS) is one of the most important source of endothelial protecting signals. Physical and chemical agents, however, including ionising radiations and anticancer drugs, may injure endothelial cells determining an increase in oxidative stress and genotoxic damage. Whether the SS protective function remains intact in the presence of strong oxidants or DNA damage is currently unclear. METHODS AND RESULTS: To investigate this aspect a series of experiments were performed in which HUVEC were exposed to sub-lethal doses of the radio-mimetic compound Bleomycin (Bleo; 10 microg/ml) which generated free radicals (ROS) without significantly compromising cell survival. Remarkably, the application of a SS of 12 dyne/cm(2) did not protect endothelial cells but markedly accelerated apoptosis compared to controls kept in static culture and in the presence of Bleo. Experiments with the inducible nitric oxide synthase (iNOS) inhibitor GW274150 significantly reduced the SS-dependent apoptosis indicating that the production of NO was relevant for this effect. At molecular level, the ataxia-telangectasia-mutated (ATM) kinase, the homeodomain-interacting protein kinase-2 (HIPK2) and p53 were found activated along a pro-apoptotic signalling pathway while p21(waf1,cip1,sdi1) was prevented from its protective action. RNA interference experiments revealed that HIPK2 and p53 were both important for this process, however, only the forced expression p21(waf1,cip1,sdi1) fully restored the SS-dependent pro-survival function. CONCLUSIONS: This study provides the first evidence that, in the presence of genotoxic damage, laminar flow contributes to endothelial toxicity and death and identifies molecular targets potentially relevant in endothelial dysfunction and cardiovascular disease pathogenesis