Steel Wire Mesh as a Thermally Resistant SERS Substrate.

In this paper, we present novel type of Surface-enhanced Raman spectroscopy (SERS) platform, based on stainless steel wire mesh (SSWM) covered with thin silver layer. The stainless steel wire mesh, typically used in chemical engineering industry, is a cheap and versatile substrate for SERS platforms. SSWM consists of multiple steel wires with diameter of tens of micrometers, which gives periodical structure and high stiffness. Moreover, stainless steel provides great resistance towards organic and inorganic solvents and provides excellent heat dissipation. It is worth mentioning that continuous irradiation of the laser beam over the SERS substrate can be a source of significant increase in the local temperature of metallic nanostructures, which can lead to thermal degradation or fragmentation of the adsorbed analyte. Decomposition or fragmentation of the analysed sample usually causea a significant decrease in the intensity of recorded SERS bands, which either leads to false SERS responses or enables the analysis of spectral data. To our knowledge, we have developed for the first time the thermally resistant SERS platform. This type of SERS substrate, termed Ag/SSWM, exhibit high sensitivity (Enhancement Factor (EF) = 106) and reproducibility (Relative Standard Deviation (RSD) of 6.4%) towards detection of p-mercaptobenzoic acid (p-MBA). Besides, Ag/SSWM allows the specific detection and differentiation between Gram-positive and Gram-negative bacterial species: Escherichia coli and Bacillus subtilis in label-free and reproducible manner. The unique properties of designed substrate overcome the limitations associated with photo- and thermal degradation of sensitive bacterial samples. Thus, a distinctive SERS analysis of all kinds of chemical and biological samples at high sensitivity and selectivity can be performed on the developed SERS-active substrate.

Studies of the synthesis of all stereoisomers of MG-132 proteasome inhibitors in the tumor targeting approach.

MG-132 is a tripeptide aldehyde (Z-l-leu-l-leu-l-leu-H, 2) proteasome inhibitor that exerts antitumor activity and enhances cytostatic/cytotoxic effects of chemo- and radiotherapy. Because of a troublesome synthesis of tripeptides with a non-natural configuration and modified side chains of amino acids, only two stereoisomers of MG-132 have been reported. Here, we propose a new approach to the synthesis of tripeptide aldehydes based on the Ugi reaction. Chiral, enantiomerically stable 2-isocyano-4-methylpentyl acetates were used as substrates for Ugi reaction resulting in a formation of tripeptide skeletons. Further functionalization of the obtained products led to a synthesis of tripeptide aldehydes. All stereoisomers of MG-132 were synthesized and studied as potential inhibitors of chymotrypsin-like, trypsin-like, and peptidylglutamyl peptide hydrolyzing activities of proteasome. These studies demonstrated the influence of absolute configuration of chiral aldehydes on the cytostatic/cytotoxic effects of the synthesized compounds and revealed that only (S,R,S)-(-)-2 stereoisomer is a more potent proteasome inhibitor than MG-132.