Low-temperature reactions: Tunnelling in space.

International audienceChemical reactions with activation barriers generally slow to a halt in the extreme cold of dense interstellar clouds. Low-temperature experiments on the reaction of OH with methanol have now shown that below 200 K there is a major acceleration in the rate that can only be explained by enhanced quantum mechanical tunnelling through the barrier

Redox-Active Nanomaterials For Nanomedicine Applications

Nanomedicine utilizes the remarkable properties of nanomaterials for the diagnosis, treatment, and prevention of disease. Many of these nanomaterials have been shown to have robust antioxidative properties, potentially functioning as strong scavengers of reactive oxygen species. Conversely, several nanomaterials have also been shown to promote the generation of reactive oxygen species, which may precipitate the onset of oxidative stress, a state that is thought to contribute to the development of a variety of adverse conditions. As such, the impacts of nanomaterials on biological entities are often associated with and influenced by their specific redox properties. In this review, we overview several classes of nanomaterials that have been or projected to be used across a wide range of biomedical applications, with discussion focusing on their unique redox properties. Nanomaterials examined include iron, cerium, and titanium metal oxide nanoparticles, gold, silver, and selenium nanoparticles, and various nanoscale carbon allotropes such as graphene, carbon nanotubes, fullerenes, and their derivatives/variations. Principal topics of discussion include the chemical mechanisms by which the nanomaterials directly interact with biological entities and the biological cascades that are thus indirectly impacted. Selected case studies highlighting the redox properties of nanomaterials and how they affect biological responses are used to exemplify the biologically-relevant redox mechanisms for each of the described nanomaterials

A quantum central limit theorem for non-equilibrium systems: Exact local relaxation of correlated states

We prove that quantum many-body systems on a one-dimensional lattice locally relax to Gaussian states under non-equilibrium dynamics generated by a bosonic quadratic Hamiltonian. This is true for a large class of initial states - pure or mixed - which have to satisfy merely weak conditions concerning the decay of correlations. The considered setting is a proven instance of a situation where dynamically evolving closed quantum systems locally appear as if they had truly relaxed, to maximum entropy states for fixed second moments. This furthers the understanding of relaxation in suddenly quenched quantum many-body systems. The proof features a non-commutative central limit theorem for non-i.i.d. random variables, showing convergence to Gaussian characteristic functions, giving rise to trace-norm closeness. We briefly relate our findings to ideas of typicality and concentration of measure.Comment: 27 pages, final versio

The inverse resonance problem for perturbations of algebro-geometric potentials

We prove that a compactly supported perturbation of a rational or simply periodic algebro-geometric potential of the one-dimensional Schr\"odinger equation on the half line is uniquely determined by the location of its Dirichlet eigenvalues and resonances.Comment: 14 page

Contextual factors among indiscriminate or larger attacks on food or water supplies, 1946-2015

This research updates previous inventories of malicious attacks on food and water to include data from 1946 through mid-2015. A systematic search of news reports, databases and previous inventories of poisoning events was undertaken. Incidents that threatened or were intended to achieve direct harm to humans, and that were either relatively large (number of victims > 4 or indiscriminate in intent or realisation were included. Agents could be chemical, biological or radio-nuclear. Reports of candidate incidents were subjected to systematic inclusion and exclusion criteria as well as validity analysis (not always clearly undertaken in previous inventories of such attacks). We summarise contextual aspects of the attacks that may be important for scenario prioritisation, modelling and defensive preparedness. Opportunity is key to most realised attacks, particularly access to dangerous agents. The most common motives and relative success rate in causing harm were very different between food and water attacks. The likelihood that people were made ill or died also varied by food/water mode, and according to motive and opportunity for delivery of the hazardous agent. Deaths and illness associated with attacks during food manufacture and prior to sale have been fewer than those in some other contexts. Valuable opportunities for food defence improvements are identified in other contexts, especially food prepared in private or community settings

Global Bounds for the Lyapunov Exponent and the Integrated Density of States of Random Schr\"odinger Operators in One Dimension

In this article we prove an upper bound for the Lyapunov exponent $\gamma(E)$ and a two-sided bound for the integrated density of states $N(E)$ at an arbitrary energy $E>0$ of random Schr\"odinger operators in one dimension. These Schr\"odinger operators are given by potentials of identical shape centered at every lattice site but with non-overlapping supports and with randomly varying coupling constants. Both types of bounds only involve scattering data for the single-site potential. They show in particular that both $\gamma(E)$ and $N(E)-\sqrt{E}/\pi$ decay at infinity at least like $1/\sqrt{E}$. As an example we consider the random Kronig-Penney model.Comment: 9 page

Positronic lithium, an electronically stable Li-e+^+ ground state

Calculations of the positron-Li system were performed using the Stochastic Variational Method and yielded a minimum energy of -7.53208 Hartree for the L=0 ground state. Unlike previous calculations of this system, the system was found to be stable against dissociation into the Ps + Li$^+$ channel with a binding energy of 0.00217 Hartree and is therefore electronically stable. This is the first instance of a rigorous calculation predicting that it is possible to combine a positron with a neutral atom and form an electronically stable bound state.Comment: 11 pages, 2 tables. To be published in Phys.Rev.Let

Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide-Extraction Properties and Metal Ion Speciation in Bis-1,2,4-Triazine Ligands

Calling all actinides! Bis-1,2,4-triazine ligands bearing five-membered rings were synthesized and evaluated as actinide-selective extractants. Tuning the size of the aliphatic ring leads to subtle changes in actinide-extraction properties. The origins of these changes were elucidated at the molecular level, paving the way for the rational design of improved actinide-selective extractants for reprocessing of spent nuclear fuel., The synthesis and evaluation of three novel bis-1,2,4-triazine ligands containing five-membered aliphatic rings are reported. Compared to the more hydrophobic ligands 1–3 containing six-membered aliphatic rings, the distribution ratios for relevant f-block metal ions were approximately one order of magnitude lower in each case. Ligand 10 showed an efficient, selective and rapid separation of AmIII and CmIII from nitric acid. The speciation of the ligands with trivalent f-block metal ions was probed using NMR titrations and competition experiments, time-resolved laser fluorescence spectroscopy and X-ray crystallography. While the tetradentate ligands 8 and 10 formed Ln$^{III}$ complexes of the same stoichiometry as their more hydrophobic analogues 2 and 3, significant differences in speciation were observed between the two classes of ligand, with a lower percentage of the extracted 1:2 complexes being formed for ligands 8 and 10. The structures of the solid state 1:1 and 1:2 complexes formed by 8 and 10 with Y$^{III}$, Lu$^{III}$ and Pr$^{III}$ are very similar to those formed by 2 and 3 with Ln$^{III}$. Ligand 10 forms Cm$^{III}$ and Eu$^{III}$ 1:2 complexes that are thermodynamically less stable than those formed by ligand 3, suggesting that less hydrophobic ligands form less stable An$^{III}$ complexes. Thus, it has been shown for the first time how tuning the cyclic aliphatic part of these ligands leads to subtle changes in their metal ion speciation, complex stability and metal extraction affinity

Leukotriene antagonists as first-line or add-on asthma controller therapy

Most randomized trials of treatment for asthma study highly selected patients under idealized conditions. METHODS: We conducted two parallel, multicenter, pragmatic trials to evaluate the real-world effectiveness of a leukotriene-receptor antagonist (LTRA) as compared with either an inhaled glucocorticoid for first-line asthma-controller therapy or a long-acting beta(2)-agonist (LABA) as add-on therapy in patients already receiving inhaled glucocorticoid therapy. Eligible primary care patients 12 to 80 years of age had impaired asthma-related quality of life (Mini Asthma Quality of Life Questionnaire [MiniAQLQ] score =6) or inadequate asthma control (Asthma Control Questionnaire [ACQ] score =1). We randomly assigned patients to 2 years of open-label therapy, under the care of their usual physician, with LTRA (148 patients) or an inhaled glucocorticoid (158 patients) in the first-line controller therapy trial and LTRA (170 patients) or LABA (182 patients) added to an inhaled glucocorticoid in the add-on therapy trial. RESULTS: Mean MiniAQLQ scores increased by 0.8 to 1.0 point over a period of 2 years in both trials. At 2 months, differences in the MiniAQLQ scores between the two treatment groups met our definition of equivalence (95% confidence interval [CI] for an adjusted mean difference, -0.3 to 0.3). At 2 years, mean MiniAQLQ scores approached equivalence, with an adjusted mean difference between treatment groups of -0.11 (95% CI, -0.35 to 0.13) in the first-line controller therapy trial and of -0.11 (95% CI, -0.32 to 0.11) in the add-on therapy trial. Exacerbation rates and ACQ scores did not differ significantly between the two groups. CONCLUSIONS: Study results at 2 months suggest that LTRA was equivalent to an inhaled glucocorticoid as first-line controller therapy and to LABA as add-on therapy for diverse primary care patients. Equivalence was not proved at 2 years. The interpretation of results of pragmatic research may be limited by the crossover between treatment groups and lack of a placebo group