Influence of buried oxide layers of nanostructured SOI surfaces on matrix-free LDI-MS performances.

In this paper, we report on the nanostructuration of the silicon crystalline top layer of different "home-made" SOI substrates presenting various buried oxide (BOx) layer thicknesses. The nanostructuration was achieved via a one-step metal assisted chemical etching (MACE) procedure. The etched N-SOI substrate surfaces were then characterized by AFM, SEM and photoluminescence. To investigate their laser desorption/ionization mass spectrometry performances, the different surfaces have been assessed towards peptide mixtures. We have shown that the matrix-free LDI process occurred from surface heating after laser irradiation and was fostered by thermal confinement in the thin nanostructured Si surface layer. This thermal confinement was enhanced with the increase of the buried oxide layer thickness until an optimal thickness of 200 nm for which the best results in terms of signal intensities, peptide discrimination and spot to spot and surface to surface variations were found.

Fast and facile preparation of nanostructured silicon surfaces for laser desorption/ionization mass spectrometry of small compounds.

RATIONALE: Many important biological processes rely on specific biomarkers (such as metabolites, drugs, proteins or peptides, carbohydrates, lipids, ...) that need to be monitored in various fluids (blood, plasma, urine, cell cultures, tissue homogenates, …). Although mass spectrometry (MS) hyphenated to liquid chromatography (LC) is widely accepted as a 'gold-standard' method for identifying such synthetic chemicals or biological products, their robust fast sensitive detection from complex matrices still constitutes a highly challenging matter. METHODS: In order to circumvent the constraints intrinsic to LC/MS technology in terms of prior sample treatment, analysis time and overall method development to optimize ionization efficiency affecting the detection threshold, we investigated laser desorption/ionization mass spectrometry (LDI-MS) by directly depositing the sample under study onto cheap inert nanostructures made of silicon to perform straightforward sensitive and rapid screening of targeted low mass biomarkers on a conventional MALDI platform. RESULTS: The investigated silicon nanostructures were found to act as very efficient ion-promoting surfaces exhibiting high performance for the detection of different classes of organic compounds, including glutathione, glucose, peptides and antibiotics. Achieving such broad detection was compulsory to develop a SALDI-MS-based pre-screening tool. CONCLUSIONS: The key contribution of the described analytical strategy consists of designing inert surfaces that are fast (minute preparation) and cheap to produce, easy to handle and able to detect small organic compounds in matrix-free LDI-MS prerequisite for biomarkers pre-screening from body fluids without the recourse of any separation step.

Toxicity Effect of Silver Nanoparticles on Photosynthetic Pigment Content, Growth, ROS Production and Ultrastructural Changes of Microalgae Chlorella vulgaris.

Silver nanoparticles (Ag NPs) exhibit antibacterial activity and are extensively used in numerous applications. The aim of this study was to examine the toxic effect of Ag NPs on the marine microalga, Chlorella vulgaris. The microalgae, at the exponential growth phase, were treated with different concentrations of Ag NPs (50 and 100 nm) for 96 h. X-Ray diffraction (XRD) results indicated that the used NPs are single and pure Ag phase with a mean crystallite size of 21 and 32 nm. Ag NPs were found to have a negative effect on viable cell concentration, a variable effect on chlorophyll a concentration, and increased ROS formation. Transmission electron microscopy (TEM) analysis revealed that Ag NPs were present inside the microalgae cells and formed large aggregates in the culture medium. Ag+ ions, in the form of AgNO3, were also assessed at higher concentrations and found to cause inhibitory effects.

Comparison of Ti-Based Coatings on Silicon Nanowires for Phosphopeptide Enrichment and Their Laser Assisted Desorption/Ionization Mass Spectrometry Detection.

We created different TiO2-based coatings on silicon nanowires (SiNWs) by using either thermal metallization or atomic layer deposition (ALD). The fabricated surfaces were characterized by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), and reflectivity measurements. Surfaces with different TiO2 based coating thicknesses were then used for phosphopeptide enrichment and subsequent detection by laser desorption/ionization mass spectrometry (LDI-MS). Results showed that the best enrichment and LDI-MS detection were obtained using the silicon nanowires covered with 10 nm of oxidized Ti deposited by means of thermal evaporation. This sample was also able to perform phosphopeptide enrichment and MS detection from serum.

MoS2/TiO2/SiNW surface as an effective substrate for LDI-MS detection of glucose and glutathione in real samples.

Here, we report for the first time, the use of molybdenum disulfide/titanium oxide/silicon nanowires (MoS2/TiO2/SiNW) surfaces for SALDI-MS detection as alternative to MALDI-MS method. Silicon nanowires were fabricated by the well-known metal-assisted chemical etching process followed by the deposition of TiO2 by atomic layer deposition. MoS2 deposition was achieved through hydrothermal treatment. The MoS2/TiO2/SiNW substrate has shown high performance for the detection of small compounds of different molecular weights, including glutathione, glucose, amino acids, antibiotics to name a few. All of the tested compounds, in pure or in mixed solutions were successfully detected in positive ion mode. Therefore, we have also attempted quantitative measurements of GSH and glucose in human blood serum.