The role of the electrolyte on the SERS spectra of pyridine

SERS spectra of pyridine has been recorded on a silver electrode in a potential range from 0.0 to -1.20 V with a saline solution, pyridine / KCl (0.1M / 0.1M), by using the 514.5 nm exciting line by us [1]. Under these experimental conditions, the maximum intensity of the enhanced 8a and 9a bands is reached at -0.75 V and -1.20 V, respectively, being the 9a band what dominates the spectrum at negative electrode potential. Although this behavior has been explained under a resonant charge transfer mechanism, the nature of the electronic resonance processes involved in the enhancement of each band is different. The 8a band is enhanced due to an electronic excitation between the ground and excited charge transfer electronic state of the metal-adsorbate surface complex, while the activity of the 9a band is due to a plasmon-like excitation taking into account an overall electronic structure of small metal clusters [2] which is able to selectively modify the relative intensities of specific SERS band. We intend now to record pyridine SERS spectra under the same experimental conditions but varying only the type of electrolyte in order to check how it affects the relative intensities and vibrational wavenumbers of the bands as well as the electrode potential to which the enhanced bands reach the maximum intensity. Different electrolytes like KCl, NaCl, KBr, NaBr and Na2SO4, have been selected in such way that allows us to compare SERS spectra in which changes only the cation or the anion of the electrolyte. From the analysis of all these SERS spectra, it can be concluded that no significant wavenumbers shifts have been detected, while the relative intensities of the bands and the electrode potential to which the maximum intensity is reached are slightly modified. NaBr electrolyte requieres more negative electrode potential in order to enhance the 8a and 9a bands and to resolve the 12 and 1 pair. Acknowledgements We are grateful to the Spanish MINECO (CTQ2012-31846) and Junta de Andalucía (FQM-5156 and 6778), for financial support. References [1] J.F. Arenas, I. López Tocón, J.C. Otero, and J.I. Marcos, J. Phys. Chem. 100, 9254-9261 (1996). [2] J. Román-Pérez, I. López-Tocón, J.L. Castro, J. F. Arenas, J. Soto and J.C. Otero, Phys. Chem. Chem. Phys.17, 2326-2329 (2015).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Existence and uniqueness of solutions of Robin's problem for the anisotriopic hyperbolic heat equation with non regular data

[EN] We find existence and uniqueness results about solutions of Robin's problem for the general anisotropic hyperbolic heat equation in the case of infinitely differentiable coefficients but irregular distributions data for the internal heat sources and boundary and initial conditions.López Molina, JA. (2018). Existence and uniqueness of solutions of Robin's problem for the anisotriopic hyperbolic heat equation with non regular data. Journal of Progressive Research in Mathematics. 13(1):21961-22031. http://hdl.handle.net/10251/165610S219612203113

Electrochemical SERS spectra of isonicotinic acid analyzed under a photoinduced charge-transfer mechanism

Isonicotinic (IN) acid is one of the three monocarboxilic derivatives of pyridine in which the acid group is located in para-position of the heterocyclic ring. It is a weak acid (pK2=4.86) and therefore, it is not completely ionized in neutral aqueous solutions, being the zwitterion and the anion the majority chemical species at neutral pH. In acidic solutions (pK1=1.84) the pyridinic nitrogen atom can be protonated yielding a third chemical species with positive charge [1]. In addition, IN acid shows two functional centres that can interact with the silver metallic surface such as the carboxilate group and the aromatic nitrogen atom. Therefore, the analysis of the SERS spectra of IN has been focused on identifying the chemical species adsorbed on the silver surface and its centre of interaction by considering the participation of a photoinduced charge-transfer (CT) mechanism in each particular SERS record as we have previously detected in the SERS of pyridine derivatives [2]. SERS spectra of the IN acid (5x10-3 M) have been recorded on silver at electrode potentials ranging from 0.00 up to -1.00 V and at different pH by using 0.1 M Na2SO4 aqueous solution as electrolyte. The figure shows the SERS recorded at basic pH. The experimental set up is described elsewhere and the excitation line of 514.5 nm wavelength was used. [2]. The detection of the presence of CT processes, which are similar to resonance Raman, requires to carry out quantum mechanical calculations [2].Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Tripod-shaped penta (p-phenylene)s for the functionalization of silicon surfaces

In order to obtain nanostructured thin films to be used in biosensor devices, several chemical functionalization methods have been developed, such as Click chemistry or Suzuki carbon-carbon coupling reactions on surfaces.1 With the aim to control the orientation and spacing between grafted functional groups on a surface, tripodal oligo (p-phenylene)s have become the ideal anisotropic adsorbates due to their shape-persistent and self-standing characteristics.2 Here we report the synthesis and characterization of several tripod-shaped oligo(p-phenylene)s molecules with legs composed of five phenylene units, compounds 1, 2 and 3. In these structures, each leg is end-capped with an NH-Boc, NH2 and N3 group, respectively. The functional arm contains an acetylene group. The presented synthesis has as key step the Pd-catalyzed Suzuki cross-coupling reaction. In particular, a iodine derivative from the silicon core molecule reacts with the appropriate tetra(p-phenylene) boron derivative, thus generating the final tripod-shaped structure. The azide end-capped leg in 3 is specifically designed for its covalent incorporation on alkynyl terminated silicon surfaces by an easy and reproducible way. As a preliminary study, we present the alkynyl-functionalized silicon wafers nanostructuration with tripod 3 through the cooper catalyzed alkyne-azide cycloaddition (CuAAC) click reaction.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Fundamentals and Applications of Surface-Enhanced Raman Spectroscopy (SERS)

When a molecule is adsorbed on some metallic nanostructured surfaces such as silver, copper or gold, it can undergo an enormous enhancement of the Raman signal giving rise to the so called Surface-Enhanced Raman Scattering (SERS). The high sensitivity of this effect allows an accurate structural study of adsorbates at very low concentrations. The SERS effect has historically been associated with the substrate roughness on two characteristic length scales. Surface roughness on the 10 to 100 nm length scale supports localized plasmon resonances which are considered as the dominant enhancement mechanism of SERS (Electromagnetic Enhancement Mechanism: SERS-EM). It is usually accepted that these electromagnetic resonances can increase the scattered intensity by an average factor of ca. 104 to 107. A secondary mechanism often thought to require atomic scale roughness is referred to as Charge Transfer (CT) Enhancement Mechanism (SERS-CT). This mechanism involves the photoinduced transfer of an electron from the metal to the adsorbate or vice versa and involves new electronic excited CT states which result from adsorbate–substrate chemical interactions. It is also estimated that such SERS-CT mechanism can enhance the scattering cross-section by a factor of ca. 10 to 102. These two mechanisms can operate simultaneously, depending on the particular systems and experimental conditions, making difficult to recognize each one and to estimate their relative magnitude in a particular spectrum.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

SERS study of different species of p-aminothiophenol adsorbed on silver nanoparticles

In the present work we have focused the discussion on the experimental and theoretical SERS spectra of the organic compound pATP recorded on silver colloids. The huge SERS of pATP on metal substrates is significantly different from its ordinary Raman spectra due to the formation of a new specie namely p,p’ –dimercaptoazobenzene (DMAB). The features of the SERS spectra of pATP are strongly dependent on many factors as i.e. the laser power density or the laser wavelength but there are still important aspects to understand as, for example, the effect of the concentration that has already been studied before by our group. In this case we have analyzed the effect of the concentration at different wavelengths on the SERS spectra of pATP on silver nanoparticles.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech