In this work, we report the detection of the organochlorine pesticides aldrin, dieldrin, lindane, and α-endosulfan by using surface-enhanced Raman spectroscopy (SERS) and optimization of the SERS-sensing substrate. In order to overcome the inherent problem of the low affinity of the above pesticides, we have developed a strategy consisting of functionalization of the metal surface with alkyl dithiols in order to achieve two different goals: (i) to induce the nanoparticle linkage and create interparticle junctions where sensitive hot spots needed for SERS enhancement are present, and (ii) to create a specific environment in the nanogaps between silver and gold nanoparticles, making them suitable for the assembly and SERS detection of the analyzed pesticides. Afterward, an optimization of the sensing substrate was performed by varying the experimental conditions: type of metal nanoparticles, molecular linker (aromatic versus aliphatic dithiols and the length of the intermediate chain), surface coverage, laser excitation wavelength. From the adsorption isotherms, it was possible to deduce the corresponding adsorption constant and the limit of detection. The present results confirm the high sensitivity of SERS for the detection of the organochlorine pesticides with a limit of detection reaching 10(-8) M, thus providing a solid basis for the construction of suitable nanosensors for the identification and quantitative analysis of this type of chemical.

A model semi-metallic brake lining was subjected to full scale automotive brake dynamometer tests. The structural properties and surface topography of brake linings were analyzed at different stages of wear testing and correlated to frictional performance. Characteristics of released wear particles were also addressed. A combination of abrasive and adhesive wear with oxidative processes dominated the friction process. Formation of a friction layer adhering to the friction surfaces of pads and discs is the major feature responsible for friction performance. Characteristics of the friction layer depend mostly on surface temperature, normal pressure, and sliding speed. It is a newly formed sintered composite matter consisting of a mixture of wear particulates. Wear rates and friction levels depend on chemistry, structure and hardness of the friction layer covering the surface of a pad or a disc; however, there is no simple Archard-type relationship between wear and measured hardness.Wear debris generated during the dynamometer tests was collected from containers placed under the brake inside dynamometer chamber. The collected debris was compared with ball-milled particles from identical brake lining. It is necessary to combine several analytical methods to characterize wear particles properly. The presence of copper and iron oxides as well as carbonaceous components is typical for all collected debris samples. Chemistry of wear debris resembles chemistry of the friction layer. Composition, mutagenic potency and pulmonary toxicity of wear debris and ball-milled particles were also analyzed. Mutagenic potency of initial friction composite and wear particles was evaluated by two in vitro bacterial microbioassays (SOS Chromotest, Ames test). Obtained results show potency of wear particles for interacting with DNA after metabolic activation, which indicates the presence of indirect mutagens. The pulmonary toxicity test on rats revealed an acute response of the lung tissue to the ball-milled particles. Further research is necessary to address the role of brake wear particles and potential impact of sub-chronic exposure to wear debris.

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Linear α,ω-dithiols have been used as linkers to control the aggregation of silver nanoparticles. The characterization of the resulting nanoparticle clusters thus formed was carried out using plasmon resonance spectroscopy and transmission electron microscopy in both independent and correlated measurements. The obtained nanoparticle assemblies present morphologies that vary according to the dithiol length, displaying controllable-size interparticle gaps (plasmonic hot spots) with potential application in the detection of a large list of hydrophobic analytes.