Detection of different species of p-aminothiophenol on silver nanoparticles by Surface-Enhanced Raman Spectroscopy (SERS)

In the present work we have analyzed the experimental and theoretical SERS spectra of the organic compound p-aminothiophenol (pATP, HS-Ph-NH2) recorded on silver nanoparticles. DFT calculations have been performed to support the experimental results in order to estimate the adsorption specie and the corresponding Raman bands assignment. It is found a different adsorption behavior of pATP not only by changing the concentration of the adsorbate but also by exciting the sample at different wavelengths.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

The effect of concentration on the Surface-Enhanced Raman Scattering of p-Aminothiophenol

The organic compound p-aminothiophenol (pATP, HS-Ph-NH2) has become very popular because it is often used for checking the enhancement capability of each new SERS substrate due to its very intense SERS spectra. SERS of pATP on silver electrode is significantly different from its ordinary Raman spectra and it is very dependent on the particular conditions of the SERS experiment. In this work the effect of adsorbate concentration on the potential dependent SERS spectra of pATP recorded on a silver electrode has been studied using NaClO4 as electrolyte. On the other hand, MS-CASPT2 have been performed in order to help the analysis of the experimental results by computing resonance Raman spectra of selected structural models of the metal−adsorbate surface complex. It is found that the spectra are dependent on adsorbate concentration and dominated by a resonant charge transfer (CT) mechanism, where the charge is always transferred from the adsorbate to the metal. The relative SERS enhancements are due to Franck−Condon factors related to the CT process, and there are not intensified bands through Herzberg−Teller contributions. Furthermore, the Raman signals of the SERS recorded at low concentration arise from at least three different molecular species: (i) pATP bonded to silver electrode through sulfur atom (Agn-S−-Ph-NH2); (ii) pATP bonded to silver electrode through both sulfur and nitrogen atoms (Agn-S−-PhNH2-Agm); (iii) The azo derivative p,p′-dimercaptoazobenzene (or its nitrene precursor).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Modelling shell and oscillation mark formation during continuous casting via explicit incorporation of slag infiltration

The development of reliable numerical models is vital to improve the quality of continuously cast products and to increase the productivity of the casting machine. In order to provide accurate predictions, these models must include detailed descriptions of the physical phenomena occurring inside the mould, such as metal flow, heat transfer and solidification. However, these topics are often treated separately during modelling due to their complexity. This has a negative impact on the accuracy of the predictions. To address this issue, a numerical model capable of coupling the flow dynamics with both the heat transfer to the mould walls and solidification has been developed. The 2‐dimenional model is based on a commercial CFD code that solves the Navier‐Stokes Equations coupled with a Volume of Fluid interface tracking technique for the multiphase system slag‐steel‐air under transient conditions within a conventional slab mould. The use of an extremely fine mesh in the meniscus region (~50 μm) allows, for the first time, the explicit calculation of liquid slag infiltration into the shell‐mould gap. Heat transfer through the solid mould faces and mould oscillation were also included in the model to provide a more realistic representation of the process. The model developed was tested in two case studies. In the first case, the predicted values were compared to prior numerical models and laboratory experiments directed to casting of conventional slabs. Excellent agreement was found for characteristics such as slag film development and heat flux variations during mould oscillation. Furthermore, predicted values for shell thickness, consumption and heat flux were also found to be in good agreement with plant measurements. The findings of this case study provided improved, fundamental understanding of the mechanisms involved in slag infiltration and solidification inside the mould and how these affect key process parameters, such as powder consumption and shell growth. The second case study consisted of a sensitivity study, where casting conditions (e.g. casting speed, mould cooling, steel/slag properties and oscillation settings) were varied in the simulations to determine their effect on both powder consumption and the formation of defects. The simulations predicted the initial formation of typical casting defects known as oscillation marks, without the aid of any external data fitting. The key result drawn from the sensitivity study was the determination of simple rules for the calculation of consumption, heat flux and defect formation as a function of the casting conditions. This opens the possibility of using the model as a diagnostic tool and for process optimisation

Simulations of GRB Jets in a Stratified External Medium: Dynamics, Afterglow Lightcurves, Jet Breaks and Radio Calorimetry

The dynamics of GRB jets during the afterglow phase is most reliably and accurately modelled using hydrodynamic simulations. All published simulations, however, have considered only a uniform external medium, while a stratified external medium is expected around long duration GRB progenitors. Here we present simulations of the dynamics of GRB jets and the resulting afterglow emission for both uniform and stratified external media with $\rho \propto r^{-k}$ for k = 0, 1, 2. The simulations are performed in 2D using the special relativistic version of the Mezcal code. The dynamics for stratified external media are broadly similar to those derived for expansion into a uniform external medium. The jet half-opening angle start increasing logarithmically with time once the Lorentz factor drops below 1/theta_0. For larger k values the lateral expansion is faster at early times and slower at late times with the jet expansion becoming Newtonian and slowly approaching spherical symmetry over progressively longer timescales. We find that contrary to analytic expectations, there is a reasonably sharp jet break in the lightcurve for k = 2 although the shape of the break is affected more by the viewing angle than by the slope of the external density profile. Steeper density profiles are found to produce more gradual jet breaks while larger viewing angles cause smoother and later appearing jet breaks. The counter-jet becomes visible as it becomes sub-relativistic, and for k=0 this results in a clear bump-like feature in the light curve. However, for larger k values the jet decelerates more gradually, causing only a mild flattening in the radio light curve that might be hard to discern when k=2. Late time radio calorimetry is likely to consistently over-estimate the true energy by up to a factor of a few for k=2, and either over-predict or under-predict it by a smaller factor for k = 0,1.Comment: 10 pages, 13 figures, submitted to Ap

Effect of graphene substrate on the SERS Spectra of Aromatic bifunctional molecules on metal nanoparticles

The design of molecular sensors plays a very important role within nanotechnology and especially in the development of different devices for biomedical applications. Biosensors can be classified according to various criteria such as the type of interaction established between the recognition element and the analyte or the type of signal detection from the analyte (transduction). When Raman spectroscopy is used as an optical transduction technique the variations in the Raman signal due to the physical or chemical interaction between the analyte and the recognition element has to be detected. Therefore any significant improvement in the amplification of the optical sensor signal represents a breakthrough in the design of molecular sensors. In this sense, Surface-Enhanced Raman Spectroscopy (SERS) involves an enormous enhancement of the Raman signal from a molecule in the vicinity of a metal surface. The main objective of this work is to evaluate the effect of a monolayer of graphene oxide (GO) on the distribution of metal nanoparticles (NPs) and on the global SERS enhancement of paminothiophenol (pATP) and 4-mercaptobenzoic acid (4MBA) adsorbed on this substrate. These aromatic bifunctional molecules are able to interact to metal NPs and also they offer the possibility to link with biomolecules. Additionally by decorating Au or Ag NPs on graphene sheets, a coupled EM effect caused by the aggregation of the NPs and strong electronic interactions between Au or Ag NPs and the graphene sheets are considered to be responsible for the significantly enhanced Raman signal of the analytes [1-2]. Since there are increasing needs for methods to conduct reproducible and sensitive Raman measurements, Grapheneenhanced Raman Scattering (GERS) is emerging as an important method [3].Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

β7 Integrin Inhibition Can Increase Intestinal Inflammation by Impairing Homing of CD25hiFoxP3+ Regulatory T Cells.

Background & aimsIntegrin α4β7 mediates lymphocyte trafficking to the gut and gut-associated lymphoid tissues, a process critical for recruitment of effector lymphocytes from the circulation to the gut mucosa in inflammatory bowel disease (IBD) and murine models of intestinal inflammation. Antibody blockade of β7 integrins generally is efficacious in IBD; however, some patients fail to respond, and a few patients can experience exacerbations. This study examined the effects of loss of β7 integrin function in murine models of IBD.MethodsIn a mouse IBD model caused by lack of interleukin 10, a cytokine important in CD25hiFoxP3+ regulatory T cell (Treg) function, genetic deletion of β7 integrin or antibody blockade of α4β7-mucosal addressin cell adhesion molecule-1 interaction paradoxically exacerbated colitis.ResultsLoss of β7 impaired the capacity of Tregs homing to the gut and therefore suppress intestinal inflammation in an adoptive T-cell transfer model; however, the intrinsic suppressive function of β7-deficient Tregs remained intact, indicating that the β7 deficiency selectively impacts gut homing. Deletion of β7 integrin did not worsen colitis in an acute dextran sodium sulfate model in which Treg number and function were normal.ConclusionsIn Integrin subunit beta (Itgb)7-/-Il10-/- mice, loss of β7-dependent Treg homing to gut-associated lymphoid tissues combined with loss of intrinsic Treg function exacerbated intestinal inflammation. These results suggest that IBD patients with reduced CD25hiFoxP3+ Treg numbers or function or lack of interleukin 10 could be at risk for failure of α4β7 blocking therapy

Conceptions of acculturation: A review and statement of critical issues

http://dx.doi.org/10.1016/j.socscimed.2011.03.01