Spectroscopies and Electron Microscopies Unravel the Origin of the First Colour Photographs

The first colour photographs were created by a process introduced by Edmond Becquerel in 1848. The nature of these photochromatic images colours motivated a debate between scientists during the XIX^th century, which is still not settled. We present the results of chemical analysis (EDX, HAXPES and EXAFS) and morphology studies (SEM, STEM) aiming at explaining the optical properties of the photochromatic images (UV‐visible spectroscopy and low loss EELS). We rule out the two hypotheses (pigment and interferences) that have prevailed since 1848, respectively based on variations in the oxidation degree of the compound forming the sensitized layer and periodically spaced photolytic silver planes. A study of the silver nanoparticles dispersions contained in the coloured layers showed specific localizations and sizes distributions of the nanoparticles for each colour. These results allow us to formulate a plasmonic hypothesis on the origin of the photochromatic images colours.     

Nanostructured Polyelectrolyte-based System as a Toolbox for Metal Ions Detection

The capability of certain heavy metal ions to induce fluorescence decrease by a quenching mechanism suggested us to design and build a sensor potentially tunable for different ions at different concentrations. We propose a quenching-based sensor exploiting a nanostructured architecture in which fluorescent molecules (the sensing probe) are entrapped to recognize a specific analyte (heavy metal ions) through an optical transduction. The polyelectrolyte nanostructured system, named nanocapsule, improves the fluorophore-ion quenching sensitivity allowing a micromolar detection. Furthermore we couple our sensor with an electrical device in order to refine the sensing procedure: the electric field created allows a metal ions spatial gradient, necessary to detect a specific element on a single sample solution, avoiding a comparative analysis with an intensity reference value. Results obtained will show the advantages and the potentialities of our system as a smart toolbox for metal ions detection.     

Optimal linear arrangements using betweenness variables

We solve for the first time to proven optimality the small instances in the classical literature benchmark of Minimum Linear Arrangement. This is achieved by formulating the problem as an ILP in a somehow unintuitive way, using variables expressing the fact that a vertex is between two other adjacent vertices in the arrangement. Using (only) these variables appears to be the key idea of the approach. Indeed, with these variables already the use of very simple constraints leads to good results, which can however be improved with a more detailed study of the underlying polytope.     

Dielectric properties of high-kappa oxides: theory and experiment for Lu2O3

We present a combined experimental and theoretical analysis of the dielectric and vibrational properties of crystalline lutetium oxide in its ground-state bixbyite structure. The vibrational dielectric function of Lu2O3 thin films grown by atomic-layer deposition was studied by infrared transmission and reflection-absorption spectroscopies, selectively accessing transverse and longitudinal optical frequencies. The static dielectric constant is extracted analyzing the infrared response. We also present first-principles density-functional linear-response calculations, which are in close agreement with experiment, and provide insight into the microscopic nature of vibrational spectra and dielectric properties.     

Synthesis of linear and tripoidal oligo(phenylene ethynylene)-based building blocks for application in modular DNA-programmed assembly

Rigid linear and tripoidal organic modules based on the oligo(phenylene ethynylene) backbone having salicylaldehyde-derived termini are synthesized. A highly functionalized 5-iodosalicyl aldehyde was prepared and coupled to each ethynyl group of 1,4-diethynylbenzene or 1,3,5-triethynylbenzene in Sonogashira couplings. The two or three termini of the compounds are functionalized for incorporation in linear and branched oligonucleotide strands. For the linear module (LM), the two termini are equipped with amide spacers, and one of these was functionalized with a DMTr (dimethoxytrityl)-protected hydroxy group and the other with a phosphoramidite. One of the tripoidal modules is prepared with DMTr groups in two of its three termini. A tripoidal module is also synthesized with three different groups on its hydroxy termini: a phosphoramidite, a DMTr group, and an Fmoc group. Extended studies have shown that these rigid linear and tripoidal organic modules can be incorporated into short oligonucleotides. Several of these modules can be applied for DNA-directed assembly and covalent coupling into structures of predetermined connectivity. Such structures have potential application for molecular electronics and nanotechnology.     

Quasielastic and inelastic neutron scattering on hydrated calcium silicate pastes

Using the inverse geometry spectrometer QENS at the Intense Pulsed Neutron Source of the Argonne National Laboratory, we collected quasielastic and inelastic neutron scattering spectra of hydrated tricalcium and dicalcium silicate, the main components of ordinary Portland cement. Data were obtained at different curing time, from a few hours to several months. Both the quasielastic and inelastic spectra have been analyzed at the same time according to the relaxing cage model, which is a model developed to describe the dynamics of water at supercooled temperatures. Short-time and long-time dynamics of hydration water in hydrated cement pastes as a function of the curing time have been simultaneously obtained. The results confirm the findings reported in previous experiments showing that it is possible to fit consistently the quasielastic and inelastic spectra giving insights on the effect of the curing time on the short-time vibrational dynamics of hydration water.     

Rheological and thermal properties of agarose aqueous solutions and hydrogels

In this article, we report on the rheological properties of agarose aqueous solutions and gels. Viscosity curves were determined for homogeneous agarose aqueous solutions at different temperatures (from 68 to 38 °C) to study the viscosity behavior as the systems undergo gelation. The gelation phenomenon of agarose solutions was also investigated by shear oscillation experiments and differential scanning calorimetry. The gelation and melting temperature as a function of agarose concentration were determined together with the gelation and melting enthalpies. The results obtained were interpreted using the two‐step model describing the gelation of agarose in water. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 322–328, 2008     

The catwalk task: Reflections and synthesis: Part 2

In this article we recount our experiences with a series of encounters with the catwalk task and reflect on the professional growth that these opportunities afforded. First, we individually reflect on our own mathematical work on the catwalk task. Second, we reflect on our experiences working with a group of community college students on the catwalk task and our interpretations of their mathematical thinking. In so doing we also detail a number of innovative and novel student-generated representations of the catwalk photos. Finally, we each individually reflect on the entire experience with the catwalk problem, as mathematics learners, as teachers, and as professionals.