Use of X-Ray Photoelectron Spectroscopy as an analytical tool for the study of contamination by Teflon in the synthesis of Mo(VI)Cl2O2Bipy/ TiO2 catalysts

The preparation of catalysts can involve various sources of contamination, which can seriously affect the quality of the prepared materials. In the present work, a case of fluorine contamination in a set of catalyst samples was studied, in which using the X-Ray Photoelectron Spectroscopy (XPS) technique, it was evidenced by the F 1s signal that this element was present in the form of Teflon, since its binding energy corresponded mainly to the CF2 species. Furthermore, using the C 1s signal, it was also possible to corroborate the presence of the CF2 group, which is associated with the main component of the Teflon carbon chains. The use of this information made it possible to identify that the solvent dehydration procedure (previous step to obtaining the catalysts) could lead to contamination with Teflon since it involved various accessories with Teflon, organic solvents and high temperature; the Teflon tape and the magnetic stirrer being the possible sources of contamination.

La preparación de catalizadores puede contener diversas fuentes de contaminación, las cuales pueden afectar seriamente las propiedades de los materiales preparados. En este artículo se estudió un caso de contaminación con flúor en una serie de muestras de catalizadores. Empleando la técnica de espectroscopia fotoelectrónica de rayos X (XPS) se evidenció la presencia de flúor en la superficie de los materiales, el cual estaba asociado al polímero teflón, ya que su energía de enlace correspondía principalmente con la de la especie CF2. Además, empleando la señal C 1s, se logró corroborar la presencia de la especie CF2, el cual está asociado al componente principal de las cadenas carbonadas de teflón. El uso de la información obtenida por XPS permitió determinar que durante la deshidratación del solvente (paso previo para la obtención de los catalizadores en el cual se emplean solventes orgánicos y alta temperatura) se podría estar llevando a cabo la contaminación con teflón, ya que este componente está presente en diversos accesorios empleados en el proceso de deshidratación, siendo la cinta de teflón y el agitador magnético las posibles fuentes de contaminación.

A preparação de catalisadores pode conter diversas fontes de contaminação, as quais podem afeitar seriamente as propriedades dos materiais preparados. No presente trabalho estudou-se um caso de contaminação com flúor numa série de amostras de catalisadores. Usando a técnica da espectroscopia fotoeletrônica de raios X (XPS), evidenciou-se a presença de flúor na superfície dos materiais, o qual estava associado ao polímero Teflon, já que sua energia de ligação correspondia principalmente à da espécie CF2. Além disso, usando a sinal C 1s, foi possível corroborar a presença do grupo CF2, o qual está associado ao componente principal das cadeias carbônicas do Teflon. O uso da informação obtida por XPS permitiu determinar que durante a desidratação do solvente (passo prévio para a obtenção dos catalisadores no qual são usados solventes orgânicos e alta temperatura) tem-se a contaminação com Teflon, já que este componente está presente em diversos acessórios utilizados no processo de desidratação, sendo a fita do Teflon e o agitador magnético as possíveis fontes da contaminação.

Thermodynamics of the Isomerization of Monoterpene Epoxides.

In this contribution, the thermodynamic analysis of α- and ß-pinene epoxide isomerization over Fe and Cu supported on MCM-41 is presented using computational chemistry and group contribution methods (GCMs). Some physical-chemical data (T c, P c, v c, Z c, ω, T b, T fus) and thermodynamic (S°298.15, C p,298.15 °, C v,298.15 °, ΔH f,298.15 °, ΔG f,298.15 °, ΔH vb °, ΔH fus, C pL) properties obtained by different GCMs are reported for several monoterpenes and monoterpenoids, which significantly contribute to the knowledge of the properties of these compounds. Density functional theory (DFT), PBE-D3/6-311G(d,p), was employed for determining the Gibbs free energy and the heat of reaction associated with the transformation of monoterpene epoxides into aldehydes, ketones, and related oxygenated compounds in the presence of different solvents and at several temperatures. The calculations were compared with available data reported and the experimental results of the catalytic reactions. The transformation of α- and ß-pinene epoxides into aldehydes appears to be more spontaneous and favorable than their transformations into alcohols in a wide range of temperatures. These results are in agreement with the experiments over Fe/MCM-41 and Cu/MCM-41, where α-pinene epoxide isomerization yields campholenic aldehyde (50-80% selectivity) as the main product. The 1.7Fe/MCM-41 material was more active in all solvents than 1.3Cu/MCM-41 for both α- and ß-pinene epoxide isomerization. However, perillyl alcohol (20-70% selectivity) was the most favored for the isomerization reaction, except when ethyl acetate was the solvent. Enthalpy and Gibbs free energy of the studied reactions estimated by both GCMs and DFT calculations did not show large differences for most of the reactions at evaluated temperatures.

Gold nanoparticle-mediated generation of reactive oxygen species during plasmonic photothermal therapy: a comparative study for different particle sizes, shapes, and surface conjugations.

Gold nanoparticle (AuNP)-mediated photothermal therapy represents an alternative to the effective ablation of cancer cells. However, the photothermal response of AuNPs must be tailored to improve the therapeutic efficacy of plasmonic photothermal therapy (PPT) and mitigate its side effects. This study presents an alternative to ease the tuning of photothermal efficiency and target selectivity. We use laser-treated spherical and anisotropic AuNPs of different sizes and biocompatible folic acid (FA)-conjugated AuNPs (FA-AuNPs) in the well-known human epithelial cervical cancer (HeLa) cell line. We show that large AuNPs produce a more significant photothermal heating effect than small ones. The thermal response of the spherical AuNPs of 9 nm was found to reach a maximum increase of 3.0 ± 1 °C, whereas with the spherical AuNPs of 14 nm, the temperature increased by over 4.4 ± 1 °C. The anisotropic AuNPs of 15 nm reached a maximum of 4.0 ± 1 °C, whereas the anisotropic AuNPs of 20 nm reached a significant increase of 5.3 ± 1 °C in the cell culture medium (MEM). Notably, the anisotropic AuNPs of 20 nm successfully demonstrate the potential for use as a photothermal agent by showing reduced viability down to 60% at a concentration of 100 µM. Besides, we reveal that high concentrations of reactive oxygen species (ROS) are formed within the irradiated cells. In combination with stress by photothermal heating, it is likely to result in significant cell death through acute necrosis by compromising the plasma membrane integrity. Cell death and ROS overproduction during PPT were characterized and quantified by transmission electron microscopy (TEM) and confocal fluorescence microscopy with different fluorescent markers. In addition, we show that FA-AuNPs induce cell death through apoptosis by internal damage, whereas diminish the ROS formation during PPT treatment. Our findings suggest the ability of plasmon-mediated ROS to sensitize cancer cells and make them vulnerable to photothermal damage, as well as the protective role of FA-AuNPs from excessive ROS formation, whereas reducing the risk of undesired side effects due to the necrotic death pathway. It allows an improvement in the efficacy of the AuNP-based photothermal therapy and a reduction in the number of exposures to high temperatures required to induce thermal stress.