Combining density functional theory (DFT) and collision cross-section (CCS) calculations to analyze the gas-phase behaviour of small molecules and their protonation site isomers

Electrospray ion mobility-mass spectrometry (IM-MS) data show that for some small molecules, two (or even more) ions with identical sum formula and mass, but distinct drift times are observed. In spite of showing their own unique and characteristic fragmentation spectra in MS/MS, no configurational or constitutional isomers are found to be present in solution. Instead the observation and separation of such ions appears to be inherent to their gas-phase behaviour during ion mobility experiments. The origin of multiple drift times is thought to be the result of protonation site isomers ('protomers'). Although some important properties of protomers have been highlighted by other studies, correlating the experimental collision cross-sections (CCSs) with calculated values has proven to be a major difficulty. As a model, this study uses the pharmaceutical compound melphalan and a number of related molecules with alternative (gas-phase) protonation sites. Our study combines density functional theory (DFT) calculations with modified MobCal methods (e.g. nitrogen-based Trajectory Method algorithm) for the calculation of theoretical CCS values. Calculated structures can be linked to experimentally observed signals, and a strong correlation is found between the difference of the calculated dipole moments of the protomer pairs and their experimental CCS separation

Vortex detection and quantum transport in mesoscopic graphene Josephson-junction arrays

We investigate mesoscopic Josephson junction arrays created by patterning superconducting disks on monolayer graphene, concentrating on the high-$T/T_c$ regime of these devices and the phenomena which contribute to the superconducting glass state in diffusive arrays. We observe features in the magnetoconductance at rational fractions of flux quanta per array unit cell, which we attribute to the formation of flux-quantized vortices. The applied fields at which the features occur are well described by Ginzburg-Landau simulations that take into account the number of unit cells in the array. We find that the mean conductance and universal conductance fluctuations are both enhanced below the critical temperature and field of the superconductor, with greater enhancement away from the graphene Dirac point.This work was financially supported by the Engineering and Physical Sciences Research Council, and an NPL/EPSRC Joint Postdoctoral Partnership (RG61493).This is the accepted manuscript. The final version is available at http://journals.aps.org/prb/abstract/10.1103/PhysRevB.91.245418

Easily retrievable objects among the NEO population

Asteroids and comets are of strategic importance for science in an effort to understand the formation, evolution and composition of the Solar System. Near-Earth Objects (NEOs) are of particular interest because of their accessibility from Earth, but also because of their speculated wealth of material resources. The exploitation of these resources has long been discussed as a means to lower the cost of future space endeavours. In this paper, we consider the currently known NEO population and define a family of so-called Easily Retrievable Objects (EROs), objects that can be transported from accessible heliocentric orbits into the Earth’s neighbourhood at affordable costs. The asteroid retrieval transfers are sought from the continuum of low energy transfers enabled by the dynamics of invariant manifolds; specifically, the retrieval transfers target planar, vertical Lyapunov and halo orbit families associated with the collinear equilibrium points of the Sun-Earth Circular Restricted Three Body problem. The judicious use of these dynamical features provides the best opportunity to find extremely low energy Earth transfers for asteroid material. A catalogue of asteroid retrieval candidates is then presented. Despite the highly incomplete census of very small asteroids, the ERO catalogue can already be populated with 12 different objects retrievable with less than 500 m/s of Δv. Moreover, the approach proposed represents a robust search and ranking methodology for future retrieval candidates that can be automatically applied to the growing survey of NEOs

Forecasting in the light of Big Data

Predicting the future state of a system has always been a natural motivation for science and practical applications. Such a topic, beyond its obvious technical and societal relevance, is also interesting from a conceptual point of view. This owes to the fact that forecasting lends itself to two equally radical, yet opposite methodologies. A reductionist one, based on the first principles, and the naive inductivist one, based only on data. This latter view has recently gained some attention in response to the availability of unprecedented amounts of data and increasingly sophisticated algorithmic analytic techniques. The purpose of this note is to assess critically the role of big data in reshaping the key aspects of forecasting and in particular the claim that bigger data leads to better predictions. Drawing on the representative example of weather forecasts we argue that this is not generally the case. We conclude by suggesting that a clever and context-dependent compromise between modelling and quantitative analysis stands out as the best forecasting strategy, as anticipated nearly a century ago by Richardson and von Neumann

Serial optical coherence microscopy for label-free volumetric histopathology

The observation of histopathology using optical microscope is an essential procedure for examination of tissue biopsies or surgically excised specimens in biological and clinical laboratories. However, slide-based microscopic pathology is not suitable for visualizing the large-scale tissue and native 3D organ structure due to its sampling limitation and shallow imaging depth. Here, we demonstrate serial optical coherence microscopy (SOCM) technique that offers label-free, high-throughput, and large-volume imaging of ex vivo mouse organs. A 3D histopathology of whole mouse brain and kidney including blood vessel structure is reconstructed by deep tissue optical imaging in serial sectioning techniques. Our results demonstrate that SOCM has unique advantages as it can visualize both native 3D structures and quantitative regional volume without introduction of any contrast agents

Spatially-resolved electronic and vibronic properties of single diamondoid molecules

Diamondoids are a unique form of carbon nanostructure best described as hydrogen-terminated diamond molecules. Their diamond-cage structures and tetrahedral sp3 hybrid bonding create new possibilities for tuning electronic band gaps, optical properties, thermal transport, and mechanical strength at the nanoscale. The recently-discovered higher diamondoids (each containing more than three diamond cells) have thus generated much excitement in regards to their potential versatility as nanoscale devices. Despite this excitement, however, very little is known about the properties of isolated diamondoids on metal surfaces, a very relevant system for molecular electronics. Here we report the first molecular scale study of individual tetramantane diamondoids on Au(111) using scanning tunneling microscopy and spectroscopy. We find that both the diamondoid electronic structure and electron-vibrational coupling exhibit unique spatial distributions characterized by pronounced line nodes across the molecular surfaces. Ab-initio pseudopotential density functional calculations reveal that the observed dominant electronic and vibronic properties of diamondoids are determined by surface hydrogen terminations, a feature having important implications for designing diamondoid-based molecular devices.Comment: 16 pages, 4 figures. to appear in Nature Material

30 days wild: development and evaluation of a large-scale nature engagement campaign to improve well-being

There is a need to increase people’s engagement with and connection to nature, both for human well-being and the conservation of nature itself. In order to suggest ways for people to engage with nature and create a wider social context to normalise nature engagement, The Wildlife Trusts developed a mass engagement campaign, 30 Days Wild. The campaign asked people to engage with nature every day for a month. 12,400 people signed up for 30 Days Wild via an online sign-up with an estimated 18,500 taking part overall, resulting in an estimated 300,000 engagements with nature by participants. Samples of those taking part were found to have sustained increases in happiness, health, connection to nature and pro-nature behaviours. With the improvement in health being predicted by the improvement in happiness, this relationship was mediated by the change in connection to nature

A CDCL-style calculus for solving non-linear constraints

In this paper we propose a novel approach for checking satisfiability of non-linear constraints over the reals, called ksmt. The procedure is based on conflict resolution in CDCL style calculus, using a composition of symbolical and numerical methods. To deal with the non-linear components in case of conflicts we use numerically constructed restricted linearisations. This approach covers a large number of computable non-linear real functions such as polynomials, rational or trigonometrical functions and beyond. A prototypical implementation has been evaluated on several non-linear SMT-LIB examples and the results have been compared with state-of-the-art SMT solvers.Comment: 17 pages, 3 figures; accepted at FroCoS 2019; software available at <http://informatik.uni-trier.de/~brausse/ksmt/