Geographical dispersal of mobile communication networks

In this paper, we analyze statistical properties of a communication network constructed from the records of a mobile phone company. The network consists of 2.5 million customers that have placed 810 million communications (phone calls and text messages) over a period of 6 months and for whom we have geographical home localization information. It is shown that the degree distribution in this network has a power-law degree distribution k⁻⁵ and that the probability that two customers are connected by a link follows a gravity model, i.e. decreases as d⁻², where d is the distance between the customers. We also consider the geographical extension of communication triangles and we show that communication triangles are not only composed of geographically adjacent nodes but that they may extend over large distances. This last property is not captured by the existing models of geographical networks and in a last section we propose a new model that reproduces the observed property. Our model, which is based on the migration and on the local adaptation of agents, is then studied analytically and the resulting predictions are confirmed by computer simulations.     

Variational fluid flow measurements from image sequences: synopsis and perspectives

Variational approaches to image motion segmentation has been an active field of study in image processing and computer vision for two decades. We present a short overview over basic estimation schemes and report in more detail recent modifications and applications to fluid flow estimation. Key properties of these approaches are illustrated by numerical examples. We outline promising research directions and point out the potential of variational techniques in combination with correlation-based PIV methods, for improving the consistency of fluid flow estimation and simulation.     

Highly sensitive and selective separation of intact parathyroid hormone and variants by sheathless CE‐ESI‐MS/MS

Parathyroid hormone (PTH) is a common clinical marker whose quantification relies on immunoassays, giving variable results as batch, brand, or target epitope changes. Sheathless CE‐ESI‐MS, combining CE resolution power and low‐flow ESI sensitivity, was applied to the analysis of PTH in its native conformation in the presence of related forms. Fused silica and neutral‐coated capillaries were investigated, as well as preconcentration methods such as transient isotachophoresis, field‐amplified sample injection (FASI), and electrokinetic supercharging (EKS). The method for the separation of PTH and its variants was first developed using fused‐silica capillary with UV detection. An acidic BGE was used to separate 1–84 PTH (full length), 7–84 PTH, and 1–34 PTH. Acetonitrile was added to the BGE to reduce peptide adsorption onto the capillary wall and transient isotachophoresis was used as analyte preconcentration method. The method was then transferred to a sheathless CE‐ESI‐MS instrument. When using a fused silica capillary, CE‐MS was limited to μg/mL levels. The use of a neutral coating combined with FASI or EKS allowed a significant increase in sensitivity. Under these conditions, 1–84 PTH, 7–84 PTH, and 1–34 PTH were detected at concentrations in the low ng/mL (FASI) or pg/mL (EKS) range.     

Volatile compounds profiling by using proton transfer reaction‐time of flight‐mass spectrometry (PTR‐ToF‐MS). The case study of dark chocolates organoleptic differences

Direct‐injection mass spectrometry (DIMS) techniques have evolved into powerful methods to analyse volatile organic compounds (VOCs) without the need of chromatographic separation. Combined to chemometrics, they have been used in many domains to solve sample categorization issues based on volatilome determination. In this paper, different DIMS methods that have largely outperformed conventional electronic noses (e‐noses) in classification tasks are briefly reviewed, with an emphasis on food‐related applications. A particular attention is paid to proton transfer reaction mass spectrometry (PTR‐MS), and many results obtained using the powerful PTR‐time of flight‐MS (PTR‐ToF‐MS) instrument are reviewed. Data analysis and feature selection issues are also summarized and discussed. As a case study, a challenging problem of classification of dark chocolates that has been previously assessed by sensory evaluation in four distinct categories is presented. The VOC profiles of a set of 206 chocolate samples classified in the four sensory categories were analysed by PTR‐ToF‐MS. A supervised multivariate data analysis based on partial least squares regression‐discriminant analysis allowed the construction of a classification model that showed excellent prediction capability: 97% of a test set of 62 samples were correctly predicted in the sensory categories. Tentative identification of ions aided characterisation of chocolate classes. Variable selection using dedicated methods pinpointed some volatile compounds important for the discrimination of the chocolates. Among them, the CovSel method was used for the first time on PTR‐MS data resulting in a selection of 10 features that allowed a good prediction to be achieved. Finally, challenges and future needs in the field are discussed.     

The mechanism of hydrogen formation induced by low-energy electron irradiation of hexadecanethiol self-assembled monolayers

The desorption of molecular hydrogen during low-energy electron irradiation of self-assembled monolayers containing n-alkanethiols has been previously reported, yet to date, there is no consensus as to the mechanism for the formation of this ubiquitous product. In this study, mixed monolayers containing known ratios of perhydrogenated and perdeuterated alkanethiols were chemisorbed to Au(111)/mica substrates and used as targets for low-energy electron irradiation; by measuring the electron-stimulated production of H(2), D(2), and HD as a function of the film composition, we unambiguously show that the desorbing molecular hydrogen is formed via a two-step bimolecular reaction process. The initial electron-molecule scattering event produces a reactive atomic fragment, which then abstracts a hydrogen atom from a nearby molecular site to produce the measured bimolecular yields; the contribution of one-step unimolecular dissociation channels to the overall molecular hydrogen yields is below the approximately 5% detection limit. The dependence of the electron-induced modifications to the film on the incident electron energy suggests that the primary event is dissociative electron attachment, and that the primary reactive fragment is most likely H(-). Quantitative analysis of the product yields shows that while approximately 80% of the molecular hydrogen is formed by this bimolecular mechanism within the film, the remaining 20% is formed from reactive atomic fragments that are ejected from the film and subsequently react with residual H(2)O adsorbed on the chamber walls.     

'On-off-on' fluorescent indicators of pH windows based on three separated components

'On-off-on' fluorescent indicators for pH windows are obtained with ternary systems in which the three separated components are Cu2+, a tetraaza ligand and the fluorophore Coumarin 343: protonation of Coumarin 343, its coordination to Cu2+ and its displacement from Cu2+ by OH- give an inverse bell-shaped variation of emission with pH.     

Modification of MCM-48-, SBA-15-, MCF-, and MSU-type mesoporous silicas with transition metal oxides using the molecular designed dispersion method

Four various mesoporous silicas (MCM-48, SBA-15, MCF, and MSU) were modified by the molecular designed dispersion method using Fe(acac)3, Cr(acac)3, and Cu(acac)2 complexes. The deposition was performed at the same concentration of the metal acetylacetonate (acac) complex in a toluene solution. All as-synthesized samples were investigated by diffuse reflectance infrared Fourier transform spectroscopy, Fourier transform infrared photoacoustic spectroscopy, and thermogravimetric analysis. The calcined materials were studied with respect to their textural properties (Brunauer-Emmett-Teller adsorption isotherm) and chemical composition (electron microprobe analysis). It allowed elucidation of the mechanism of interaction between the acac complex and the silanol groups. For the MCM-48, SBA-15, and MCF materials, the formation of hydrogen bonding was found for the chromium- and copper-modified samples, whereas the Fe-containing materials showed the ligand exchange mechanism. The strong interaction of the MSU support and the different acetylacetonate complexes, resulting in a loss of at least one acac ligand, was observed. The mesoporous silicas modified with transition metal oxides were studied by UV-vis-DR spectroscopy. The different metal dispersions were found for the samples containing various transition metal oxides.     

Approximation of the Distribution of the Supremum of a Centered Random Walk. Application to the Local Score

Let (X _n ) _{n 0} be a real random walk starting at 0, with centered increments bounded by a constant K. The main result of this study is: |P(S _n n x)–P( sup_{0 u 1} B _u x)| C(n,K) n/n, where x 0, ² is the variance of the increments, S _n is the supremum at time n of the random walk, (B _u ,u 0) is a standard linear Brownian motion and C(n,K) is an explicit constant. We also prove that in the previous inequality S _n can be replaced by the local score and sup₀ u 1 B _u by sup₀ u 1|B _u |.     

Short-time dynamics through conical intersections in macrosystems

The short-time dynamics through a conical intersection of a macrosystem with a vast number of nuclear degrees of freedom (modes) is investigated. For convenience, the macrosystem is decomposed into a system carrying a few modes and a "bath." By transforming the bath modes to new ones, it is shown that only three effective bath modes contribute to the conical intersection. They govern--together with the system's modes--the short-time dynamics of the macrosystem. The remaining bath modes do not directly couple the electronic states and become relevant at longer times. An extensive numerical example is presented.