Polypyrrole (PPy) nanorods (NRs) and nanoparticles (NPs) are synthesized via electrochemical and chemical methods, respectively, and tested upon ammonia exposure using Raman and X-ray photoelectron spectroscopy (XPS). Characterization of both nanomaterials via Raman spectroscopy demonstrates the formation of PPy, displaying vibration bands consistent with the literature. Additionally, XPS reveals the presence of neutral PPy species as major components in PPy NRs and PPy NPs, and other species including polarons and bipolarons. Raman and XPS analysis after ammonia exposure show changes in the physical/chemical properties of PPy, confirming the potential of both samples for ammonia sensing. Results demonstrate that the electrochemically synthesized NRs involve both proton and electron transfer mechanisms during ammonia exposure, as opposed to the chemically synthesized NPs, which show a mechanism dominated by electron transfer. Thus, the different detection mechanisms in PPy NRs and PPy NPs appear to be connected to the particular morphological and chemical composition of each film. These results contribute to elucidate the mechanisms involved in ammonia detection and the influence of the synthesis routes and the physical/chemical characteristics of PPy.

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Mass spectrometry imaging (MSI) is a molecular imaging technique that maps the distribution of molecules in biological tissues with high spatial resolution. The most widely used MSI modality is matrix-assisted laser desorption/ionization (MALDI), mainly due to the large variety of analyte classes amenable for MALDI analysis. However, the organic matrices used in classical MALDI may impact the quality of the molecular images due to limited lateral resolution and strong background noise in the low mass range, hindering its use in metabolomics. Here we present a matrix-free laser desorption/ionization (LDI) technique based on the deposition of gold nanolayers on tissue sections by means of sputter-coating. This gold coating method is quick, fully automated, reproducible, and allows growing highly controlled gold nanolayers, necessary for high quality and high resolution MS image acquisition. The performance of the developed method has been tested through the acquisition of MS images of brain tissues. The obtained spectra showed a high number of MS peaks in the low mass region (m/z below 1000 Da) with few background peaks, demonstrating the ability of the sputtered gold nanolayers of promoting the desorption/ionization of a wide range of metabolites. These results, together with the reliable MS spectrum calibration using gold peaks, make the developed method a valuable alternative for MSI applications.

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This paper presents a unique perspective on enhancing the physicochemical mechanisms of two distinct highly sensitive nanostructured metal oxide micro hot plate gas sensors by utilizing an innovative multifrequency interrogation method. The two types of sensors evaluated here employ an identical silicon transducer geometry but with a different morphological structure of the sensitive film. While the first sensing film consists of self-ordered tungsten oxide nanodots, limiting the response kinetics of the sensor-chemical species pair only to the reaction phenomena occurring at the sensitive film surface, the second modality is a three-dimensional array of tungsten oxide nanotubes, which in turn involves both the diffusion and adsorption of the gas during its reaction kinetics with the sensitive film itself. By utilizing the proposed multifrequency interrogation methodology, we demonstrate that the optimal temperature modulation frequencies employed for the nanotubes-based sensors to selectively detect hydrogen, carbon monoxide, ethanol, and dimethyl methyl phosphonate (DMMP) are significantly higher than those utilized for the nanodot-based sensors. This finding helps understand better the amelioration in selectivity that temperature modulation of metal oxides brings about, and, most importantly, it sets the grounds for the nanoengineering of gas-sensitive films to better exploit their practical usage.