Multiplexed CuAAC Suzuki-Miyaura Labeling for Tandem Activity-Based Chemoproteomic Profiling.

Mass-spectrometry-based chemoproteomics has enabled the rapid and proteome-wide discovery of functional and potentially 'druggable' hotspots in proteins. While numerous transformations are now available, chemoproteomic studies still rely overwhelmingly on copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) or 'click' chemistry. The absence of bio-orthogonal chemistries that are functionally equivalent and complementary to CuAAC for chemoproteomic applications has hindered the development of multiplexed chemoproteomic platforms capable of assaying multiple amino acid side chains in parallel. Here, we identify and optimize Suzuki-Miyaura cross-coupling conditions for activity-based protein profiling and mass-spectrometry-based chemoproteomics, including for target deconvolution and labeling site identification. Uniquely enabled by the observed orthogonality of palladium-catalyzed cross-coupling and CuAAC, we combine both reactions to achieve dual labeling. Multiplexed targeted deconvolution identified the protein targets of bifunctional cysteine- and lysine-reactive probes

Assessment of Ag Nanoparticles Interaction over Low-Cost Mesoporous Silica in Deep Desulfurization of Diesel

Chemical interactions between metal particles (Ag or Ni) dispersed in a low-cost MCM-41M produced from beach sand amorphous silica and sulfur compounds were evaluated in the deep adsorptive desulfurization process of real diesel fuel. N2 adsorption-desorption isotherms, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy coupled to energy-dispersive X-ray spectroscopy (STEM-EDX) were used for characterizing the adsorbents. HRTEM and XPS confirmed the high dispersion of Ag nanoparticles on the MCM-41 surface, and its chemical interaction with support and sulfur compounds by diverse mechanisms such as π-complexation and oxidation. Thermodynamic tests indicated that the adsorption of sulfur compounds over Ag(I)/MCM-41M is an endothermic process under the studied conditions. The magnitude of ΔH° (42.1 kJ/mol) indicates that chemisorptive mechanisms govern the sulfur removal. The best fit of kinetic and equilibrium data to pseudo-second order (R2 > 0.99) and Langmuir models (R2 > 0.98), respectively, along with the results for intraparticle diffusion and Boyd’s film-diffusion kinetic models, suggest that the chemisorptive interaction between organosulfur compounds and Ag nanosites controls sulfur adsorption, as seen in the XPS results. Its adsorption capacity (qm = 31.25 mgS/g) was 10 times higher than that obtained for pure MCM-41M and double the qm for the Ag(I)/MCM-41C adsorbent from commercial silica. Saturated adsorbents presented a satisfactory regeneration rate after a total of five sulfur adsorption cycles