Adsorption of dye molecules on metallic nanoparticles: Unraveling the origins of the modified spectral absorption

<p>The enhanced optical response of molecules in the vicinity of metallic nanoparticle is the basis for many surface enhanced spectroscopies and of interest to the field of plasmonics. However, the mechanisms behind the enhancement are still a matter of debate because of the interplay between electromagnetic and chemical effects, which complicates the interpretation of spectral changes. Our ability to measure the surface absorption of dyes from very low coverage to high coverage allows us to identify the con- tribution of each effect (dye-dye interaction and dye-particle interaction) to the spectral modifications. In the course of this investigation, we also measured the adsorption isotherms of dyes in the presence of halide ions, which provides a detailed insight into the adsorption process on silver colloids.</p>

Adsorption of dye molecules on metallic nanoparticles: Unraveling the origins of the modified spectral absorption

<p>The enhanced optical response of molecules in the vicinity of metallic nanoparticle is the basis for many surface enhanced spectroscopies and of interest to the field of plasmonics. However, the mechanisms behind the enhancement are still a matter of debate because of the interplay between electromagnetic and chemical effects, which complicates the interpretation of spectral changes. Our ability to measure the surface absorption of dyes from very low coverage to high coverage allows us to identify the con- tribution of each effect (dye-dye interaction and dye-particle interaction) to the spectral modifications. In the course of this investigation, we also measured the adsorption isotherms of dyes in the presence of halide ions, which provides a detailed insight into the adsorption process on silver colloids.</p>

Non-Radiative Processes and Vibrational Pumping in Surface-Enhanced Raman Scattering

<p><b>The main focus of this thesis was the physical interpretation of the pumping cross-section. This was achieved by performing a statistical analysis of single molecule vibrational pumping events in which both the SERS and pumping cross-sections could be measured simultaneously. Samples were constructed in which small aggregates of silver colloids were evenly distributed on a dry surface.</b></p> <p>The sample was then cooled to 77K so that the main mechanism for creating a vibrational population was through Stokes scattering. Spatial mappings were then performed which measured how the SERS spectrum varied with positionon the sample and the single molecule events were identified. The SERS cross-sections were determined from the Stokes intensity while the pumping cross-sections were determined from the ratio of the anti-Stokes and Stokes peaks. It was observed that the pumping cross-section was often significantly larger than the SERS cross-section, as much as four orders of magnitude in some cases. Several attempts were made to explain this discrepancy including the possibility ofthe surface plasmon resonance favouring anti-Stokes scattering, underestimated lifetimes for the vibrational modes, and additional pumping from fluorescence. However, the most likely candidate was non-radiative Stokes scattering by the observed molecule which would increase the vibrational population but would not increase the Stokes intensity. To estimate the proportion of scattered light that is radiative or non-radiative,single molecule measurements were performed under both surface-enhanced and unmodified conditions. By comparing the fluorescence and Raman intensities under these scenarios, it was possible to estimate the radiative and non-radiative enhancement factors. It was found that the non-radiative SERS cross-section was typically much larger than the radiative cross-section for samples consisting of aggregated silver colloids. The discrepancy between the pumping and SERS cross-section (which is the radiative cross-section) could therefore be explained by non-radiative scattering dominating the creation of the vibrational population, along with an additional contribution due to the plasmon resonance favouring certain vibrational modes. Furthermore, the lifetime of a molecule after it has been excited to the first electronic state was estimated to be as short as 25 fs. It would be impossible to measure lifetimes of this order of magnitude in single molecules using time-resolved techniques. Furthermore, to the very best of our knowledge, this is the first time that an experimental determination of the non-radiative SERS cross-section has been made.</p>

Non-Radiative Processes and Vibrational Pumping in Surface-Enhanced Raman Scattering

<p><b>The main focus of this thesis was the physical interpretation of the pumping cross-section. This was achieved by performing a statistical analysis of single molecule vibrational pumping events in which both the SERS and pumping cross-sections could be measured simultaneously. Samples were constructed in which small aggregates of silver colloids were evenly distributed on a dry surface.</b></p> <p>The sample was then cooled to 77K so that the main mechanism for creating a vibrational population was through Stokes scattering. Spatial mappings were then performed which measured how the SERS spectrum varied with positionon the sample and the single molecule events were identified. The SERS cross-sections were determined from the Stokes intensity while the pumping cross-sections were determined from the ratio of the anti-Stokes and Stokes peaks. It was observed that the pumping cross-section was often significantly larger than the SERS cross-section, as much as four orders of magnitude in some cases. Several attempts were made to explain this discrepancy including the possibility ofthe surface plasmon resonance favouring anti-Stokes scattering, underestimated lifetimes for the vibrational modes, and additional pumping from fluorescence. However, the most likely candidate was non-radiative Stokes scattering by the observed molecule which would increase the vibrational population but would not increase the Stokes intensity. To estimate the proportion of scattered light that is radiative or non-radiative,single molecule measurements were performed under both surface-enhanced and unmodified conditions. By comparing the fluorescence and Raman intensities under these scenarios, it was possible to estimate the radiative and non-radiative enhancement factors. It was found that the non-radiative SERS cross-section was typically much larger than the radiative cross-section for samples consisting of aggregated silver colloids. The discrepancy between the pumping and SERS cross-section (which is the radiative cross-section) could therefore be explained by non-radiative scattering dominating the creation of the vibrational population, along with an additional contribution due to the plasmon resonance favouring certain vibrational modes. Furthermore, the lifetime of a molecule after it has been excited to the first electronic state was estimated to be as short as 25 fs. It would be impossible to measure lifetimes of this order of magnitude in single molecules using time-resolved techniques. Furthermore, to the very best of our knowledge, this is the first time that an experimental determination of the non-radiative SERS cross-section has been made.</p>

Sonoelectrochemical Synthesis of Silver Nanoparticles in Sodium Polyacrylate Solution

The paper shows the effectiveness of a “green” synthesis of silver nanoparticles (AgNPs) in sodium polyacrylate (NaPA) solutions by sonoelectrochemical method using silver sacrificial anodes. Using the cyclic voltammetry in the ultrasonic field in the range of E from 1.0 to -1.0 V, the temperature and NaPA concentration are the main parameters influencing the rate of synthesis and the size of AgNPs. As these parameters increase, the rate of nanoparticle synthesis increases. According to TEM studies, with increasing temperature and decreasing NaPA concentration, there is a tendency to increase the size of AgNPs. However, in all of the cases, the size of AgNPs does not exceed 30 nm. Using the UV–Vis spectroscopy, it was found that the position of the absorption peak at c.a. 500 nm, corresponding to the silver nanoparticles, is practically not shifted during numerous cycles. This fact may indicate the stability of sonoelectrochemical synthesis of AgNPs in time. Synthesized AgNPs revealed high antibacterial activity against gram-positive and gram-negative strains of typical pathogens of nosocomial infections, demonstrating the prospect of using sonoelectrochemical technique for obtaining silver colloids as a component of bactericidal drugs.

Optomechanical Processing of Silver Colloids: New Generation of Nanoparticle–Polymer Composites with Bactericidal Effect

The properties of materials at the nanoscale open up new methodologies for engineering prospective materials usable in high-end applications. The preparation of composite materials with a high content of an active component on their surface is one of the current challenges of materials engineering. This concept significantly increases the efficiency of heterogeneous processes moderated by the active component, typically in biological applications, catalysis, or drug delivery. Here we introduce a general approach, based on laser-induced optomechanical processing of silver colloids, for the preparation of polymer surfaces highly enriched with silver nanoparticles (AgNPs). As a result, the AgNPs are firmly immobilized in a thin surface layer without the use of any other chemical mediators. We have shown that our approach is applicable to a broad spectrum of polymer foils, regardless of whether they absorb laser light or not. However, if the laser radiation is absorbed, it is possible to transform smooth surface morphology of the polymer into a roughened one with a higher specific surface area. Analyses of the release of silver from the polymer surface together with antibacterial tests suggested that these materials could be suitable candidates in the fight against nosocomial infections and could inhibit the formation of biofilms with a long-term effect.