RESUMO
Straightforward analysis of chemical processes on the nanoscale is difficult, as the measurement volume is linked to a discrete number of molecules, ruling out any ensemble averaging over rotation and diffusion processes. Raman spectroscopy is sufficiently selective for monitoring chemical changes, but is not sufficiently sensitive to be applied directly. Surface-enhanced Raman spectroscopy (SERS) can be applied for studying reaction kinetics, but adds additional variability in the signal as the enhancement factor is not the same for every location. A novel chemometric method described here separates reaction kinetics from short-term variability, based on the lack of fit in a principal-component analysis. We show that it is possible to study effects that occur on different time scales independently without data reduction using the photocatalytic reduction of p-nitrothiophenol as a showcase system. Using this approach a better description of the nanoscale reaction kinetics becomes available, while the short-term variations can be examined separately to examine reorientation and/or diffusion effects. It may even be possible to identify reaction intermediates through this approach. With only a limited number of reactive molecules in the studied volume, an intermediate on a SERS hot spot may temporarily dominate the spectrum. Now such events can be easily separated from the bulk conversion process by making use of this chemometric method.
RESUMO
We have developed a new easy-to-use probe that can be used to combine atomic force microscopy (AFM) and scanning near-field optical microscopy (SNOM). We show that, using this device, the evanescent field, obtained by total internal reflection conditions in a prism, can be visualized by approaching the surface with the scanning tip. Furthermore, we were able to obtain simultaneous AFM and SNOM images of a standard test grating in air and in liquid. The lateral resolution in AFM and SNOM mode was estimated to be 45 and 160 nm, respectively. This new probe overcomes a number of limitations that commercial probes have, while yielding the same resolution.
RESUMO
The applicability of confocal Raman microscopy for characterizing thin liquid-crystal (LC) filled polymer capsules obtained by photo-enforced stratification is demonstrated. The investigated structure consists of an array of polymer capsules (typical size 500 x 500 x 20 microm) filled with LC material and is made by photopolymerization of a mixture of monomers and LC. Such an array can be used as the electro-optical component in liquid crystal displays. Confocal Raman microscopy does not require complex sample preparation, is non-invasive, and is shown to have adequate spatial and depth resolution. Although Raman spectroscopy is inherently insensitive, the use of data preprocessing and computational modeling makes it possible to quantify both the conversion of monomer to polymer and the compositions of both the polymer-rich and the LC-rich phase.
RESUMO
In this paper Raman spectrometry is introduced in the field of sealed battery research for in situ gas-phase analysis and for longterm measurements. For this purpose, a new method was successfully applied in order to model battery behavior without interfering with operation. It is shown that oxygen, hydrogen, and nitrogen are responsible for the pressure increase that occurs during overcharging. The relative contribution of the different gases depends on the current imposed on the battery as well as the operating temperature. Reproducible and stable signals could be obtained even under severe conditions such as high pressure and elevated temperature. Oxygen and hydrogen are produced in side reactions taking place during battery operation. However, as nitrogen is unlikely to be a reacting gas inside the battery, the change in its partial pressure can be attributed to electrode expansion and a change in the electrolyte volume.
