Nano-Raman spectroscopy with side-illumination optics

We describe an apertureless near-field Raman spectroscopy setup that has successfully produced substantial enhancements for a wide variety of samples and achieved a high contrast. The tremendous potential of tip-enhanced Raman spectroscopy (TERS) for nanoscale chemical characterization has been demonstrated by various groups by measuring organic dyes, biological molecules, single-walled carbon nanotubes and silicon. Keys to rapid advances in the application of TERS to pressing scientific problems include the optimization of the method to achieve greater reproducibility and greater enhancement factors if possible, but more importantly, greater imaging contrast. Using a side-illumination geometry, we demonstrate reproducible enhancements of the Raman signal per volume on the order of 10³–10⁴ using silver- and gold-coated tips on various molecular, polymeric and semiconducting materials as well as on carbon nanotubes. We have experimentally verified localization of the enhancement to a depth of ∼20 nm. Most importantly, optimization of the polarization geometry makes possible a contrast between the near-field and far-field signals of 900% in the case of silicon—a level that makes the technique attractive for various applications. Copyright © 2005 John Wiley & Sons, Ltd.     

Magnetic Nanoparticle Thermometry via Controlled Diffusion

The process of magnetic nanoparticle heating releases enormous amounts of thermal energy. Through typical calorimetric analyses, the total thermal energy released can be easily quantified; however, knowledge of nanoscale temperature is necessary. Herein, a novel method of nanoscale thermometry by analyzing intra-particle diffusion in core–shell nanoparticles is proposed. Heating the iron cores with an alternating magnetic field in a saline suspension encourages the diffusion of sodium ions into the silica shells of the particles, which is modeled numerically; however, experimental measurements are needed in order to provide accurate diffusivity estimations. After determining the diffusion characteristics from X-ray photoelectron spectroscopy) depth profiling of silica films, energy dispersive analysis with high-resolution transmission electron microscopy measures the sodium ion gradient within single particles before and after heating. When compared directly to the numerical simulations, the results indicate that the temperature gradient between particles and saline suspension reaches significantly higher temperatures than the macro-scale temperature of the solution. By accurately knowing the thermal gradient between nanoparticles and the surrounding medium, nanoparticles can be engineered to limit surface resistances as much as possible and promote high rates of thermal energy transfer.     

Raman spectral analysis of renal tissue: a novel application

Renal cell carcinoma (RCC) accounts for 85% of all primary renal cancers. The definitive diagnosis of RCC relies exclusively on the subjective pathological interpretation of the surgical specimen. In this study, we aimed to analyze renal tissue using objective Raman spectroscopy (RS). We obtained 15 pairs of RCC (T) and corresponding normal renal parenchymal tissues (N) from our biobank. There are three subtypes of RCC: clear cell RCC (ccRCC), papillary RCC (pRCC), and chromophobe RCC (cRCC). Five pairs of tissue of each subtype were enrolled. Fresh‐frozen sliced tissues were used for the RS detection. The Raman spectra between T and N were compared and analyzed using partial least squares (PLS) regression. Data for a total of 55 T and 58 N analyzable RS samples were obtained. The spectra were normalized by dividing the intensity of the characteristic peak at 1003 cm⁻¹ using phenylalanine's Raman peak. After further analysis with PLS, the sensitivity and specificity for discriminating T from N were 95% and 93%, respectively. The RCC subtypes can be discriminated at an accuracy of 72% for ccRCC, 88% for cRCC, and 86% for pRCC. This study demonstrates the feasibility of analyzing renal tissue using RS. RS, with its advantages of easy and objective tissue assessment, may be applied to aid intraoperative decision making and pathological tissue assessment. Copyright © 2014 John Wiley & Sons, Ltd.