We demonstrate the use of a scanning transmission electron microscope (STEM) equipped with a monochromator and an electron energy loss (EEL) spectrometer as a powerful tool to study localized surface plasmons in metallic nanoparticles. We find that plasmon modes can be influenced by changes in nanostructure geometry and electron beam damage and show that it is possible to delineate the two effects through optimization of specimen preparation techniques and acquisition parameters. The results from the experimental mapping of bright and dark plasmon energies are in excellent agreement with the results from theoretical modeling.
Human’s quest for innovation, finding solutions of problems, and upgrading the industrial yield with energy efficient and cost-effective materials has opened the avenues of nanotechnology. Among a variety of nanoparticles, zinc oxide nanoparticles (ZnO) have advantages because of the extraordinary physical and chemical properties. It is one of the cheap materials in cosmetic industry, nanofertilizers, and electrical devices and also a suitable agent for bioimaging and targeted drug and gene delivery and an excellent sensor for detecting ecological pollutants and environmental remediation. Despite inherent toxicity of nanoparticles, synthetic routes are making use of large amount of chemical and stringent reactions conditions that are contributing as environmental contaminants in the form of high energy consumption, heat generation, water consumption, and chemical waste. Further, it is also adding to the innate toxicity of nanoparticles (NPs) that is either entirely ignored or poorly investigated. The current review illustrates a comparison between pollutants and hazards spawned from chemical, physical, and biological methods used for the synthesis of ZnO. Further, the emphasis is on devising eco-friendly techniques for the synthesis of ZnO especially biological methods which are comparatively less hazardous and need to be optimized by controlling the reaction conditions in order to get desired yield and characteristics.
The demonstration that quantitative and sensitive analysis can be carried out using surface enhanced resonance Raman scattering (SERRS) prompted a discussion and investigation of the main variables which are within the control of the analyst using colloidal silver as the substrate. Previous papers have dealt with the crucial need to obtain good chemisorption of the analyte to the surface and have reported the use of specially designed dyes for SERRS. One of the most variable processes is the aggregation of the colloid. Here, we investigate the addition of controlled amounts of an organic aggregating agent, poly-L-lysine, at concentrations which reduce the zeta potential in a controlled manner, thus aiding aggregation control. The relationship between the excitation frequency, the surface plasmon resonance frequency of the silver colloid and the frequency of the maximum absorbance of the molecular chromophore is studied using low concentrations of dye and no aggregating agent. Under these conditions, little to no aggregation is expected. The magnitude of the enhancement is strongly dependent on the frequency of the molecular chromophore as well as the plasmon resonance frequency. However, when sodium chloride is used to aggregate the colloid, a larger enhancement is obtained and the strong dependence on the molecular chromophore largely disappears. A much broader enhancement profile is obtained which appears to be related more to the specific enhancement processes caused by aggregation than the frequency of the chromophore. However, the total enhancement for SERRS is higher than for SERS thus indicating that the chromophore is still important to the process.
Effective correlation of data from a number of analytical techniques over length scales spanning several orders of magnitude is required to more fully investigate the active sites on silver nanoparticles that are responsible for surface-enhanced resonance Raman scattering (SERRS). In this paper, a method is presented that uses fluorescent beads as optical markers to allow direct correlation between a SERRS/fluorescence map and a transmission electron microscope (TEM) collage of the same area. Factors influencing the accuracy of the technique include the flatness of the substrate, the size of the fluorescent beads, and the strength of the signal from the fluorescent beads. When the effect of each of these factors on the technique is addressed, a simple and accurate correlation between the optical spectroscopy and the electron microscopy is achieved. A statistically significant number of particles can then be easily and reliably located and characterized at both optical limits, by SERRS, and with subnanometer resolution in the high-resolution TEM. Examples of HRTEM images and the locations of these particles within the SERRS map/TEM collage are presented. Our findings reveal that the relative SERRS activity of single particles is very low compared to dimers and larger aggregates of particles. The relative activity of dimers is estimated to be 12.4 times greater than single particles, and as the number of particles in the aggregate increase, the relative SERRS activity also increases. The relative SERRS activities of single particles/dimers/trimers/aggregates of 4-9 particles/aggregates of 10-20 are estimated to be 1/12.4/15.6/23.2/43.
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