Raman Study of the Stability of Biomolecules on Lichens After Space - and Mars Like Conditions: Mission Ground Reference (MGR) Samples

The main objectives of BIOMEX [1,2] project are, on the one hand, to analyze the resistance of terrestrial extremophiles to survive in outer space and in Mars-like environment, and on the other hand, to deep into the stability under space and Mars-like conditions of biomolecules. For that reason, samples of the extremophile lichen Circinaria gyrosa (C. gyrosa) [3, 4] has been selected and included in the BIOMEX experiment. After the exposure on the EXPOSE-R2 facility at the ISS during 15 months, a correlative Mission Ground Experiment (MGR) reproducing EXPOSE R2 conditions was performed: selected samples of C. gyrosa were exposed to simulated Mars-like and Space-like environments reproduced at the space- and planetary chambers of DLR-Cologne in order to study Mars’ habitability and resistance to real space conditions. These samples defined as Mission Ground Reference (MGR) samples, have been analyzed in order to search for biomarkers and pigments at the inner part, containing the medulla and algal clusters.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

SERS study of thiocarbonyl compounds adsorbed on metal nanoparticles

Thiocarbonyl compounds have been reported to exhibit interesting biological and pharmacological properties but they are many often characterized by their toxicological effects. However the chemistry of thiobenzoic acid (TBA) and thiobenzamide (TB) has not been fully studied yet. Some of the biological studies of TBA are related to the tautomerism of thiocarboxylic acids and the important role that the -C(=O)-S and -C(=S)-O functional groups play in the catalytic activities of enzymes such as cysteine or serine proteases.1 On the other hand, TB and derivatives are well known hepatotoxins and have been used as inhibitor in enzymatic reactions and in pharmacy due to their microbial activity.2 From a chemical point of view, thiocarboxylates are an interesting type of molecules having two different donor atoms, a soft sulfur donor atom and a hard oxygen donor one. The presence of these unlike groups can lead to the bonding with metal surfaces. Likewise the interaction of thiobenzamide and their derivatives with metals is of great interest because both the sulfur and nitrogen atoms are also able to coordinate with the surface. Therefore the high affinity of these molecules for metal surfaces makes them suitable SERS target adsorbates. Taking advantage of the fact that SERS spectroscopy is both surface selective and highly sensitive we have attempted to determine the molecular structure of TBA and TB once they are adsorbed on the metal. The main objective of this work is focussed on discussing the observed vibrational wavenumber shifts of TBA and TB upon adsorption on silver nanoparticles. In this work the SERS substrates have been prepared by using different colloidal silver solutions according to the method described by Creighton et al.3 and Leopold and Lendl.4 The analysis of the vibrational wavenumbers shifts of the Raman and SERS spectra allow us to know the adsorption process (Figure 1). In the case of TBA, the wavenumber of the SERS band assigned to (C=O) vibrational mode shows an important blue shift up to 40 cm-1 with respect to the Raman whereas the (C-S) band undergoes a red shift up to 40 cm-1. These results suggest a unidentate coordination of TBA to the silver surface through the sulfur atom. On the other hand, the SERS band assigned in the case of TB to Amide III (mainly (CN)) exhibits a significant blueshift up to 41 cm-1, and the SERS band assigned to Amide I (mainly (CS)) shows a red shift up to 11 cm-1. These wavenumber shifts indicate that TB interacts to the silver surface through the sulfur atom. Interestingly, in previous SERS studies of pyridinecarboxamides and benzamide we have observed that some SERS bands assigned to 1;ring, Amide I (mainly (C=O)) and Amide III (mainly C-N)) show wavenumber shifts of +50, -50 and +10 cm-1, respectively, which were attributed to the deprotonation of carboxamide group.5,6 Finally, in order to verify experimental results DFT calculations have been carried out for different silver complexes of TBA and TB concluding that the unidentate coordination is the most likely interaction of both of them.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Una asignatura on-line de Historia de los Algoritmos

This paper describes the objectives, contents learning methodology and results of an on-line course about History of Algorithms for engineering students of the Polytechnic University of Madrid. This course is conducted in a virtual environment based on Moodle, with an educational model centered at student which includes a detailed planning of learning activities. . Our experience indicates that this subject is is highly motivating for students and the virtual environment facilitates competencies development

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

Modeling the effect of the electrode potential in SERS by electronic structure calculations.

Surface Enhanced Raman Spectroscopy (SERS), due to the ability of greatly intensify the weak Raman signal of molecules adsorbed to metal surfaces, has proven to be a very useful tool to investigate changes in the electronic structure of metal-molecule surface complex. A deep knowledge of the electronic structure of these metal-molecule hybrid systems is key in electrochemistry, catalysis, plasmonics, molecular electronics, and in the development of selective and ultra-sensitive analytical sensors. The origin of this huge enhancement in SERS is due to two contributions: the electromagnetic (EM), related to surface plasmons, and the chemical mechanism, due to resonant charge transfer (CT) process between the adsorbate and the metal (CTSERS). Unfortunately, the SERS implies very complex phenomena where the molecule and the metal nanoparticle are involved. This fact makes challenging to build realistic theoretical models that take into account both the metal and the molecule at quantum level. We propose a methodology, based on DFT and ab initio electronic calculations, to simulate the effect of the electrode potential on the absorption, on the charge transfer states energies, and on the electronic excitations in metal-molecule hybrid systems from a microscopic point of view. This methodology consists on the prediction of Raman intensities from ab initio calculations of the geometries or the energy gradients at the excited states Franck-Condon point, bringing the possibility to predict the intensities in CTSERS as well as in resonance Raman without the need to know the excited state geometries, not always feasible to compute. The microscopic model adopted to mimic the effect of the interphase electric potential consist in a molecule adsorbed to a linear silver cluster [Agn-Adsorbate]q, were n is the number of silver atoms, and the total charge of the system (q) is zero for n=2 and q=±1 for n=1, 3 and 7.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Surface-Enhanced Raman spectroscopy of thiobenzoic acid on metal nanoparticles

Molecules adsorbed on some metal surfaces such as silver, copper and gold, can exhibit enormous Surface-enhanced Raman Scattering (SERS). The SERS effect has historically been associated with substrate roughness on two characteristic length scales [1,2]. Surface roughness on the 10 to 100 nm length scale supports the electromagnetic resonances which are the dominant mechanism of enhancement. A second mechanism often thought to require atomic scale roughness, is referred to as the chemical enhancement mechanism. This second mechanism involves the creation of new electronic excited states which result from adsorbate–substrate chemical interactions. These two mechanisms operate simultaneously making it difficult to isolate the role and magnitude of each one. In this work the SERS spectra of thiobenzoic acid (TBA) adsorbed on several silver colloids are recorded by using different excitation wavelengths. Taking advantage of the fact that SERS spectroscopy is both, surface selective and highly sensitive, we have attempted to determine the molecular structure of the surface complex once TBA is adsorbed on the metal. The analysis of the vibrational wavenumbers of the Raman and SERS spectra suggests that this molecule shows unidentate coordination to the silver surface through the sulphur atom. In order to confirm this conclusion DFT calculations have been carried out for different TBA-silver complexes concluding that the unidentate coordination is the most likely interaction of TBA on the metal surface. Wavelength-scanned SERS excitation spectroscopy involves the measurement of SERS signal by using several excitation wavelengths and it was recognized as a useful tool for checking the mechanisms responsible for the SERS enhancement [3]. We have studied the effect of the wavelength within the SERS spectra of TBA on silver colloid prepared by different methods and we have analyzed the intensity of the 8a vibrational mode of TBA recorded at about 1590 cm-1. The intensity of this mode is noticeably higher in the spectrum recorded with the 514.5 nm line (Fig. 1). This result is attributed to the presence of a resonant Raman effect associated to a photoinduced charge-transfer process when using the most energetic excitation line. Finally, it is important to mention the high affinity of TBA for the silver surfaces what allows for a detection limit estimated to be 0.01 microM.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Raman, SERS and DFT study of chemically-adsorbed thiobenzoic acid on silver nanoparticles

Thiocarboxylic acids are organosulphur compounds with general formula RC(O)SH. They are related to carboxylic acids by the replacement of one oxygen by sulphur. Two tautomers are possible, written as RC(S)OH and RC(O)SH. The second one is the majority species in solid state and solution of thiobenzoic acid (TBA) at room temperature [1], but derivatives from both tautomers are known so that the SERS spectrum can be originated by either one. Taking advantage of the fact that SERS spectroscopy is both surface selective and highly sensitive we have attempted to determine the molecular structure of TBA once it is adsorbed on the metal surface. To accomplish this SERS spectra of TBA have been recorded on different silver colloids. A combination of layer-by-layer method with spin-coating deposition of silver nanoparticles have been used to prepare SERS active substrates on which the homogeneity of the SERS signal of TBA has been analyzed. Fig. 1 (I) shows the Raman spectra of TBA in the neat liquid (a), 1 M aqueous solution at pH 14 (b), SERS spectrum of a 5x10-4 M silver colloid prepared by reduction of silver nitrate with sodium borohydride at pH 7 (c) and SERS spectrum of a 5x10-4 M silver colloid prepared by reduction of silver nitrate with hydroxylamine hydrochloride (d). The assignment of the Raman spectra has been based on the present work as well as on previous studies [2-4]. The two bands recorded at 1662 and 2572 cm-1 in Fig.1a, are assigned to (C=O) and (SH) modes, what confirms that the Raman spectrum in the neat liquid is due to the thiolic specie of TBA, RC(O)SH. In the Raman spectrum of the solution (Fig. 1b) a significant redshift of (C=O) mode of 52 cm-1 and the absence of the (SH) band are detected in agreement with the behavior observed in the SERS spectrum (Fig. 1c). The latter confirms that the thiol tautomer of thiobenzoate anion, RC(O)S-, is adsorbed on silver nanoparticles. Other important SERS enhancements have been registered for the following vibrational modes: 8a;ring, (C=O) and (CS) recorded at 1592, 1554 and 928 cm-1 in Fig. 1c and 1d, respectively. The last two modes, (C=O) and (CS), undergo wavenumber shifts of +40 and -40 cm-1 respectively, which are closely related with the coordination of thiobenzoate anion to the metal surface [5]. The analysis of the vibrational wavenumber of these modes suggests that this molecule shows unidentate coordination through the sulphur atom to the metal surface. In order to confirm this fact DFT calculations have been carried out for different silver complexes: I) bridging bidentate ligand, (II) chelating ligand and (III and IV) unidentate ligand (Fig. 2). Theoretical wavenumber of representative bands of these compounds have been compared to the experimental one concluding that the behavior of the unidentate ligand (III) is the most probably coordination type of TBA on the metal surface. In order to confirm these conclusions the SERS spectra of TBA on silver colloid prepared by reduction of silver nitrate with hydroxylamine hydrochloride at different concentration of analyte have been recorded as well (Fig. 1 (II)). It is well known that the SERS enhancement factor depends strongly on different factors and in particular on the adsorption properties of the probe and the analyte concentration on the surface coverage. In this sense TBA has shown a very good detection level for this particular silver colloid it being a highly SERS active molecule. The detection limit is estimated to be 0.01 molar. Finally, Fig. 3 shows a representative Raman mapping of TBA adsorbed on a silver substrate prepared by spin-coating. Generally speaking, the image represents a fairly homogeneous distribution of the SERS intensity highlighting some points where the intensity is stronger as is expected in areas with heterogeneous coverage. The reproducibility of this type of substrate is under study focusing their application as reproducible and ultrasensitive sensing assemblies by using TBA as the target molecule due its good SERS sensitivity.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Distress intolerance and pain catastrophizing as mediating variables in PTSD and chronic noncancer pain comorbidity.

Objectives: Several studies have demonstrated posttraumatic stress disorder (PTSD) and chronic pain comorbidity. However, there is a lack of research on the psychological variables that might explain their co-occurrence. We investigated the mediating role of distress intolerance and pain catastrophizing in this relationship. Methods: A moderated mediation model was tested. The sample comprised 114 individuals with chronic noncancer pain (90 women and 24 men; mean age, of 60.04 years [SD=9.76]). Results: Catastrophizing had a significant effect on PTSD. Distress intolerance mediated catastrophizing and PTSD, and pain intensity moderated this relationship. Conclusions: New insights are provided into the psychological variables that may explain PTSD and chronic noncancer pain comorbidity