Challenges investigating molecules on plasmonic nanostructures have limited understanding of these interactions. However, the chemically specific information in the surface-enhanced Raman scattering (SERS) spectrum can identify perturbations in the adsorbed molecules to provide insight relevant to applications in sensing, catalysis, and energy conversion. Here, we demonstrate spectrally resolved SERS imaging, to simultaneously image and collect the SERS spectra from molecules adsorbed on individual nanoparticles. We observe intensity and frequency fluctuations in the SERS signal on the time scale of tens of milliseconds from n -mercaptobenzoic acid (MBA) adsorbed to gold nanoparticles. The SERS signal fluctuations correlate with density functional theory calculations of radicals generated by the interaction between MBA and plasmon-generated hot electrons. Applying localization microscopy to the data provides a super-resolution spectrally resolved map that indicates the plasmonic-induced molecular charging occurs on the extremities of the nanoparticles, where the localized electromagnetic field is reported to be most intense.

In this study, perfluorinated phosphonic acid modifications were utilized to modify zinc oxide (ZnO) nanoparticles because they create a more stable surface due to the electronegativity of the perfluoro head group. Specifically, 12-pentafluorophenoxydodecylphosphonic acid, 2,3,4,5,6-pentafluorobenzylphosphonic acid, and (1H,1H,2H,2H-perfluorododecyl)phosphonic acid have been used to form thin films on the nanoparticle surfaces. The modified nanoparticles were then characterized using infrared spectroscopy, X-ray photoelectron spectroscopy, and solid-state nuclear magnetic resonance spectroscopy. Dynamic light scattering and scanning electron microscopy-energy dispersive X-ray spectroscopy were utilized to determine the particle size of the nanoparticles before and after modification, and to analyze the film coverage on the ZnO surfaces, respectively. Zeta potential measurements were obtained to determine the stability of the ZnO nanoparticles. It was shown that the surface charge increased as the alkyl chain length increases. This study shows that modifying the ZnO nanoparticles with perfluorinated groups increases the stability of the phosphonic acids adsorbed on the surfaces. Thermogravimetric analysis was used to distinguish between chemically and physically bound films on the modified nanoparticles. The higher weight loss for 12-pentafluorophenoxydodecylphosphonic acid and (1H,1H,2H,2H-perfluorododecyl)phosphonic acid modifications corresponds to a higher surface concentration of the modifications, and, ideally, higher surface coverage. While previous studies have shown how phosphonic acids interact with the surfaces of ZnO, the aim of this study was to understand how the perfluorinated groups can tune the surface properties of the nanoparticles.

Melanoma, a type of cancer that develops in melanocytes, is usually caused by direct exposure of skin to ultraviolet (UV) radiation resulting in cellular damage. In this study, a procedure to determine the effects of various commercial sunscreens with SPF values ranging from 15 to 100 was developed using pig skin to mimic human skin. These sunscreens contain inorganic filters, such as zinc oxide and titanium dioxide; active organic ingredients, such as octocrylene and oxybenzone; or both. As a model for human skin, pig skin was analyzed before and after UV exposure, and the presence of free radicals was measured using electron paramagnetic resonance (EPR) spectroscopy. Using this method, students were able to quantify radical formation following irradiation and use this as a basis to compare the efficacies of sunscreens against UVA. This experiment allowed undergraduate students to characterize a complex chemical process (light-induced radical formation) and relate it to something they experience every day (sun damage). Interestingly, students found higher levels of postillumination radical formation in sunscreen-treated samples, perhaps indicating sunscreen-induced stabilization of these species. Student outcomes included learning how to collect and interpret EPR data, statistical analysis of these data, and the preparation of reproducible biological samples. Students also consulted literature sources to properly display their measurements.

High spatial resolution imaging and chemicalspecific detection in living organisms is important in a wide range of fields from medicine to catalysis. In this work, we characterize a wide-field surface-enhanced Raman scattering (SERS) imaging approach capable of simultaneously capturing images and SERS spectra from nanoparticle SERS tags in cancer cells. By passing the image through a transmission diffraction grating before it reaches an array detector, we record the image and wavelength dispersed signal simultaneously on the camera sensor. Optimization of the experiment provides an approach with better spectral resolution and more rapid acquisition than liquid crystal tunable filters commonly used for wide-field SERS imaging. Intensity fluctuations inherent to SERS enabled localization algorithms to be applied to both the spatial and spectral domain, providing super-resolution SERS images that are correlated with improved peak positions identified in the spectrum of the SERS tag. The detected Raman signal is shown to be sensitive to the focal plane, providing three-dimensional (3D) sectioning abilities for the detected nanoparticles. Our work demonstrates spectrally resolved super-resolution SERS imaging that has the potential to be applied to complex physical and biological imaging applications.

The excitation of plasmon resonances on nanoparticles generates locally enhanced electric fields commonly used for sensing applications, and energetic charge carriers can drive chemical transformations as photocatalysts. The surface-enhanced Raman scattering (SERS) spectra from mercaptobenzoic acid (MBA) adsorbed to gold nanoparticles (AuNP) and silica-encapsulated gold nanoparticles (AuNP@silica) can be used to assess the impact of energetic charge carriers on the observed signal. Measurements were recorded using a traditional point-focused Raman spectroscopy and a wide-field spectral imaging approach to assess changes in the spectra of the different particles at increasing power density. The wide-field approach provides an increase in sampling statistics and shows evidence of SERS frequency fluctuations from MBA at low power densities, where it is commonly difficult to record spectra from a point-focused spot. The increased spectral resolution of the point spectroscopy measurement provides improved peak identification and the ability to correlate the frequency fluctuations to charged intermediate species. Interestingly, our work suggests that isolated nanoparticles may undergo frequency fluctuations more readily than aggregates.

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With the advancements in broad-spectrum sunscreens and the recent bans on benzene-based sunscreens due to their environmental toxicity, there has been a push toward broad-spectrum sunscreens containing inorganic active ingredients. In this study, a procedure was developed to analyze the particle size and size distribution of inorganic active ingredients, titanium dioxide (TiO2) and/or zinc oxide (ZnO), of sunscreens with sun protection factor (SPF) values ranging from 15 to 50 using dynamic light scattering (DLS). These inorganic components are often engineered as nanoparticles in order to reduce visibility on the skin and retain UV scattering. Research suggests that the use of smaller nanoparticles to increase the efficacy of the inorganic filters may also be toxic to humans if it becomes permeable to the skin. This methodology allowed undergraduate students to work hands-on with particle sizing and compare sunscreen samples to nanopowder and dispersion standards using the effect of the hydrodynamic diameter. Students found that, due to agglomeration, the particle sizes for the nanopowder standards could exceed the manufacture’s labeled size when dispersed in solution, which they then compared with their sunscreen data. The results also showed that some sunscreens had two distinct layers at the end of sample preparation, which could be correlated to the matrix components within the sunscreens. This study is intended for undergraduate analytical students and can be altered using the potential variations and scanning electron microscopy (SEM) with electron dispersive spectroscopy (EDS) to create a more challenging upper-level lab and allow for instrumentation comparisons.

Advances in nanotechnology enable the detection of trace molecules from the enhanced Raman signal generated at the surface of plasmonic nanoparticles. We have developed technology to enable super-resolution imaging of plasmonic nanoparticles, where the fluctuations in the surface enhanced Raman scattering (SERS) signal can be analyzed with localization microscopy techniques to provide nanometer spatial resolution of the emitting molecule’s location. Additional work now enables the super-resolved SERS image and the corresponding spectrum to be acquired simultaneously. Here we will discuss how this approach can be applied to provide new insights into biological cells.