Chemical and Mineralogical Analysis of Samples Using Combined LIBS, Raman Spectroscopy and µ-EDXRF

Energy-dispersive X-ray fluorescence (EDXRF) analysis is one of the standard techniques for the evaluation of mineral deposits. The advantage of EDXRF is the fast delivery of information about the bulk elemental composition as well as the elemental composition of each mineral class. With micro energy-dispersive X-ray fluorescence (µ-EDXRF) analysis, information can be obtained with a micrometer resolution. However, it has some limitations. With EDXRF, light elements (e.g., lithium) cannot be detected, and the count rates for carbon, fluorine and sodium are very low. This might lead to a misinterpretation of the mineral classes and the worth of the deposit. Furthermore, the identification of the alteration phases of primary minerals is ambiguous. Here, we will present an approach to overcome the limitations of µ-EDXRF by complementing it with combined laser-induced breakdown spectroscopy (LIBS) and Raman spectroscopy. In contrast to EDXRF, LIBS is able to detect all elements, including light elements. Raman spectroscopy can identify mineral phases and eventually provide additional information on their alterations and modifications. In the present paper, we show results for two different samples covering a certain chemical and mineralogical range that demonstrate the potential of the proposed combination of methods for the chemical and mineralogical analysis of geological samples

Surface-enhanced Raman spectroscopy for the analysis of smokeless gunpowders and macroscopic gunshot residues

Gunshot residues (GSR) result from the discharge of a firearm being a potential piece of evidence in criminal investigations. The macroscopic GSR particles are basically formed by burned and non-burned gunpowder. Motivated by the demand of trace analysis of these samples, in this paper, the use of surface-enhanced Raman scattering (SERS) was evaluated for the analysis of gunpowders and macroscopic GSR particles. Twenty-one different smokeless gunpowders were extracted with ethanol. SERS spectra were obtained from the diluted extracts using gold nanoaggregates and an excitation wavelength of 633 nm. They show mainly bands that could be assigned to the stabilizers diphenylamine and ethylcentralite present in the gunpowders. Then, macroscopic GSR particles obtained after firing two different ammunition cartridges on clothing were also measured using the same procedure. SERS allowed the detection of the particles collected with an aluminum stub from cloth targets without interferences from the adhesive carbon. The results demonstrate the great potential of SERS for the analysis of macroscopic GSR particles. Furthermore, they indicate that the grain-to-grain inhomogeneity of the gunpowders needs to be considered.European Commission-Prevention of and Fight against Crime Programme Ministerio de Educación, Cultura y Deport

Biomolecular environment, quantification, and intracellular interaction of multifunctional magnetic SERS nanoprobes

Multifunctional composite nanoprobes consisting of iron oxide nanoparticles linked to silver and gold nanoparticles, Ag–Magnetite and Au–Magnetite, respectively, were introduced by endocytic uptake into cultured fibroblast cells. The cells containing the non-toxic nanoprobes were shown to be displaceable in an external magnetic field and can be manipulated in microfluidic channels. The distribution of the composite nanostructures that are contained in the endosomal system is discussed on the basis of surface-enhanced Raman scattering (SERS) mapping, quantitative laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) micromapping, and cryo soft X-ray tomography (cryo soft-XRT). Cryo soft-XRT of intact, vitrified cells reveals that the composite nanoprobes form intra-endosomal aggregates. The nanoprobes provide SERS signals from the biomolecular composition of their surface in the endosomal environment. The SERS data indicate the high stability of the nanoprobes and of their plasmonic properties in the harsh environment of endosomes and lysosomes. The spectra point at the molecular composition at the surface of the Ag–Magnetite and Au–Magnetite nanostructures that is very similar to that of other composite structures, but different from the composition of pure silver and gold SERS nanoprobes used for intracellular investigations. As shown by the LA-ICP-MS data, the uptake efficiency of the magnetite composites is approximately two to three times higher than that of the pure gold and silver nanoparticles.Peer Reviewe

Gold nanoisland substrates for SERS characterization of cultured cells.

To access publisher's full text version of this article, please click on the hyperlink in Additional Links field or click on the hyperlink at the top of the page marked DownloadWe demonstrate a simple approach for fabricating cell-compatible SERS substrates, using repeated gold deposition and thermal annealing. The substrates exhibit SERS enhancement up to six orders of magnitude and high uniformity. We have carried out Raman imaging of fixed mesenchymal stromal cells cultured directly on the substrates. Results of viability assays confirm that the substrates are highly biocompatible and Raman imaging confirms that cell attachment to the substrates is sufficient to realize significant SERS enhancement of cellular components. Using the SERS substrates as an in vitro sensing platform allowed us to identify multiple characteristic molecular fingerprints of the cells, providing a promising avenue towards non-invasive chemical characterization of biological samples.Icelandic Centre for Research Haskoli Islands European Research Council (ERC

pH-Dependent Flavin Adenine Dinucleotide and Nicotinamide Adenine Dinucleotide Ultraviolet Resonance Raman (UVRR) Spectra at Intracellular Concentration

The ultraviolet resonance Raman spectra of the adenine-containing enzymatic redox cofactors nicotinamide adenine dinucleotide and flavin adenine dinucleotide in aqueous solution of physiological concentration are compared with the aim of distinguishing between them and their building block adenine in potential co-occurrence in biological materials. At an excitation wavelength of 266 nm, the spectra are dominated by the strong resonant contribution from adenine; nevertheless, bands assigned to vibrational modes of the nicotinamide and the flavin unit are found to appear at similar signal strength. Comparison of spectra measured at pH 7 with data obtained pH 10 and pH 3 shows characteristic changes when pH is increased or lowered, mainly due to deprotonation of the flavin and nicotinamide moieties, and protonation of the adenine, respectively.Bundesministerium für Bildung und Forschung https://doi.org/10.13039/501100002347European Commission https://doi.org/10.13039/501100000780Senate Chancellery of the federal state of BerlinMinistry of Culture and Science of the state of North Rhine-WestfaliaDeutsche Forschungsgemeinschaft https://doi.org/10.13039/501100001659Peer Reviewe

Optical properties of silver nanocube surfaces obtained by silane immobilization

Silver nanocubes were synthesized by the polyol method and immobilized on a surface in a simple approach using an aminopropyltriethoxysilane (APTES). The optical and structural properties of the polyvinylpyrrolidone (PVP) stabilized nanocubes were investigated in solution and on glass surfaces. The SERS enhancement factors at two excitation wavelengths for crystal violet were compared with electric fields arising in different nano¬particle configurations using finite-difference time-domain simulations. They are in agreement with the preferred face-to-face orientation in the nanoaggregates on the surfaces. The facile immobilization enables on-demand preparation and use of the nanocubes in real analytical applications

Role of Metal Cations in Plasmon-Catalyzed Oxidation: A Case Study of <i>p</i>‑Aminothiophenol Dimerization

The mechanism of the plasmon-catalyzed reaction of <i>p</i>-aminothiophenol (PATP) to 4,4′-dimercaptoazobenzene (DMAB) on the surface of metal nanoparticles has been discussed using data from surface-enhanced Raman scattering of DMAB. Oxides and hydroxides formed in a plasmon-catalyzed process were proposed to play a central role in the reaction. Here, we report DMAB formation on gold nanoparticles occurring in the presence of the metal cations Ag⁺, Au³⁺, Pt⁴⁺, and Hg²⁺. The experiments were carried out under conditions where formation of gold oxide or hydroxide from the nanoparticles can be excluded and at high pH where the formation of the corresponding oxidic species from the metal ions is favored. On the basis of our results, we conclude that, under these conditions, the selective oxidation of PATP to DMAB takes place via formation of a metal oxide from the ionic species in a plasmon-catalyzed process. By evidencing the necessity of the presence of the metal cations, the reported results underpin the importance of metal oxides in the reaction

Single-Particle Plasmon Sensing of Discrete Molecular Events: Binding Position versus Signal Variations for Different Sensor Geometries

The sensitivity of a surface plasmon to the dielectric environment makes it a viable tool in detecting single molecules. To be able to precisely determine sensed molecular concentrations and carry out precise analyses of single-molecule binding/unbinding events in real time it is necessary to quantify rigorously the relation between the number of bound molecules and the spectral response of the plasmonic sensor. However, this is challenging as this relation is subject to an uncertainty which is highly dependent on the spatially varying response of the plasmonic nanosensor of choice. The origin of this uncertainty is little understood, and its effect is often disregarded in quantitative sensing experiments. Here, we employ stochastic diffusion-reaction simulations of biomolecular interactions on a sensor’s surface combined with electromagnetic calculations of the plasmon resonance peak shift of three metal nanosensors (disk, cone, dimer) to clarify the interplay between position-dependent binding probability and inhomogeneous sensitivity distribution in determining the statistical characteristics of the total signal upon molecular binding. This approach is generally applicable regardless of the specific transduction mechanism at the basis of sensing. Here we identify how this interplay affects the feasibility of using certain plasmonic sensors for sensing low concentrations or real-time monitoring of individual binding reactions and how illumination conditions may affect the level of uncertainty of the measured signal upon molecular binding