Tracking the formation of eumelanin from L-Dopa using coupled measurements

Melanin plays a crucial role as a pigment all through the animal kingdom. Being a macromolecule just on the divide between an ordered crystalline or a purely amorphous form melanin has proven a challenge to structure-function analysis. Melanin assembles from small molecules much like a jigsaw and much like in a jigsaw the fine detail quickly vanishes in the overall picture. With melanin being first and foremost a photo-active molecule we focus on spectral properties for the characterisation of its structure. We use absorption measurements to illustrate the complex nature of the formation process. To gain a better hold on the formation pathway we use coupled measurements of excitation and emission to identify 'areas of interest' in the excitation-emission matrix (EEM). We then probe one area for characteristic fluorescence lifetimes to track one melanin building block through the formation process. Comparison of the EEMs of L-Dopa derived melanin with natural Sepia melanin shows characteristic differences. We show how the presence of copper ions creates a melanin closer to its natural form

Mapping the formation of eumelanin using coupled measurements

Melanin plays a crucial role as a pigment all through the animal kingdom. Being a macromolecule just on the divide between an ordered crystalline or a purely amorphous form melanin has proven a challenge to structure-function analysis. Melanin assembles from small molecules much like a jigsaw and much like in a jigsaw the fine detail quickly vanishes in the overall picture. With Melanin being first and foremost a photo-active molecule we focus on spectral properties for the characterization of its structure using linked measurements of excitation and emission to identify ‘areas of interest’ in the Excitation-Emission Matrix (EEM). We then probe for characteristic fluorescence lifetimes in the identified areas to track melanin building blocks through the formation pathway

It is Hobbes, not Rousseau:an experiment on voting and redistribution

We perform an experiment which provides a laboratory replica of some important features of the welfare state. In the experiment, all individuals in a group decide whether to make a costly effort, which produces a random (independent) outcome for each one of them. The group members then vote on whether to redistribute the resulting and commonly known total sum of earnings equally amongst themselves. This game has two equilibria, if played once. In one of them, all players make effort and there is little redistribution. In the other one, there is no effort and nothingWe thank Iris Bohnet, Tim Cason, David Cooper, John Duffy, Maia Guell, John Van Huyck and Robin Mason for helpful conversations and encouragement. The comments of the Editor and two referees helped improve the paper. We gratefully acknowledge the financial support from Spain’s Ministry of Science and Innovation under grants CONSOLIDER INGENIO 2010 CSD2006-0016 (all authors), ECO2009-10531 (Cabrales), ECO2008-01768 (Nagel) and the Comunidad de Madrid under grant Excelecon (Cabrales), the Generalitat de Catalunya and the CREA program (Nagel), and project SEJ2007-64340 of Spain’s Ministerio de Educación y Ciencia (Rodríguez Mora).Publicad

Influence of ions and pH on formation of solid and liquid-like melanin

Melanin is a natural pigment with broadband absorption and effective ability to dissipate the energy absorbed. The macromolecular structure of melanin shows a delicate balance between short-range ordered and disordered structures without being a random aggregate. The presence of ions or the variation in pH or ionic strength can alter the self-assembly process which subsequently changes the structure of melanin. To understand these relationships, this study investigates the influence of ions and pH in melanin formation. The types of ions present and pH have a profound influence on the formation and structure of melanin particles, while only minor changes are observed in the absorption and excitation-emission analysis. In some conditions, the formation of discernible particles with significant refractive index contrast is avoided while retaining the spectroscopic characteristics of melanin, leading to liquid-like melanin. These findings identify potential pathways which can be used to manipulate the melanin macromolecular structure while providing the desired spectral properties to enable novel bio-engineering applications.

Revealing the photophysics of gold-nanobeacons via time-resolved fluorescence spectroscopy

We demonstrate that time-resolved fluorescence spectroscopy is a powerful tool to investigate the conformation states of hairpin DNA on the surface of gold nanoparticles (AuNPs) and energy transfer processes in Au-nanobeacons. Long-range fluorescence quenching of Cy5 by AuNPs has been found to be in good agreement with electrodynamics modelling. Moreover, time-correlated single-photon counting (TCSPC) is shown to be promising for real-time monitoring of the hybridization kinetics of Au-nanobeacons, with up to 60% increase in decay time component and 300% increase in component fluorescence fraction observed. Our results also indicate the importance of the stem and spacer designs for the performance of Au-nanobeacons

Scaling of the specific heat in superfluid films

We study the specific heat of the $x-y$ model on lattices $L \times L \times H$ with $L \gg H$ (i.e. on lattices representing a film geometry) using the Cluster Monte--Carlo method. In the $H$--direction we apply Dirichlet boundary conditions so that the order parameter in the top and bottom layers is zero. We find that our results for the specific heat of various thickness size $H$ collapse on the same universal scaling function. The extracted scaling function of the specific heat is in good agreement with the experimentally determined universal scaling function using no free parameters.Comment: 4 pages, uuencoded compressed PostScrip

On the use of core-shell type semiconductor nanocrystals as sensors

Here we describe progress towards our objective of non contact transition metal ion sensing. Semiconductor nanocrystals show complex photophysical properties and require a very careful setup of the measurement parameters. Under these conditions they allow for very high resolution sensing of ions

Towards single metal ion sensing by Förster resonance energy transfer

Here we describe progress towards our objective of detecting single non-fluorescent hydrated metal ions

Barrier-free subsurface incorporation of 3d metal atoms into Bi(111) films

By combining scanning tunneling microscopy with density functional theory it is shown that the Bi(111) surface provides a well-defined incorporation site in the first bilayer that traps highly coordinating atoms such as transition metals (TMs) or noble metals. All deposited atoms assume exactly the same specific sevenfold coordinated subsurface interstitial site while the surface topography remains nearly unchanged. Notably, 3d TMs show a barrier-free incorporation. The observed surface modification by barrier-free subsorption helps to suppress aggregation in clusters. It allows a tuning of the electronic properties not only for the pure Bi(111) surface, but may also be observed for topological insulators formed by substrate-stabilized Bi bilayers. © 2015 American Physical Society.DFG/SFB/616DFG/SPP/1601DFG/Pf238/3

Galaxy Clusters as Reservoirs of Heavy Dark Matter and High-Energy Cosmic Rays: Constraints from Neutrino Observations

Galaxy Clusters (GCs) are the largest reservoirs of both dark matter and cosmic rays (CRs). Dark matter self-annihilation can lead to a high luminosity in gamma rays and neutrinos, enhanced by a strong degree of clustering in dark matter substructures. Hadronic CR interactions can also lead to a high luminosity in gamma rays and neutrinos, enhanced by the confinement of CRs from cluster accretion/merger shocks and active galactic nuclei. We show that IceCube/KM3Net observations of high-energy neutrinos can probe the nature of GCs and the separate dark matter and CR emission processes, taking into account how the results depend on the still-substantial uncertainties. Neutrino observations are relevant at high energies, especially at >10 TeV. Our results should be useful for improving experimental searches for high-energy neutrino emission. Neutrino telescopes are sensitive to extended sources formed by dark matter substructures and CRs distributed over large scales. Recent observations by Fermi and imaging atmospheric Cherenkov telescopes have placed interesting constraints on the gamma-ray emission from GCs. We also provide calculations of the gamma-ray fluxes, taking into account electromagnetic cascades inside GCs, which can be important for injections at sufficiently high energies. This also allows us to extend previous gamma-ray constraints to very high dark matter masses and significant CR injections at very high energies. Using both neutrinos and gamma rays, which can lead to comparable constraints, will allow more complete understandings of GCs. Neutrinos are essential for some dark matter annihilation channels, and for hadronic instead of electronic CRs. Our results suggest that the multi-messenger observations of GCs will be able to give useful constraints on specific models of dark matter and CRs. [Abstract abridged.]Comment: 31 pages, 20 figures, 1 table, accepted for publication in JCAP, references and discussions adde