RESUMO
This study critically reevaluates reported Biginelli-like reactions using a Kamlet-Abboud-Taft-based solvent effect model. Surprisingly, structural misassignments were discovered in certain multicomponent reactions, leading to the identification of pseudo three-component derivatives instead of the expected MCR adducts. Attempts to replicate literature conditions failed, prompting reconsideration of the described MCRs and proposed mechanisms. Electrospray ionization (tandem) mass spectrometry, NMR, melting points, elemental analyses and single-crystal X-ray analysis exposed inaccuracies in reported MCRs and allowed for the proposition of a complete catalytic cycle. Biological investigations using both pure and "contaminated" derivatives revealed distinctive features in assessed bioassays. A new cellular action mechanism was unveiled for a one obtained pseudo three-component adduct, suggesting similarity with the known dihydropyrimidinone Monastrol as Eg5 inhibitors, disrupting mitosis by forming monoastral mitotic spindles. Docking studies and RMSD analyses supported this hypothesis. The findings described herein underscore the necessity for a critical reexamination and potential corrections of structural assignments in several reports. This work emphasizes the significance of rigorous characterization and critical evaluation in synthetic chemistry, urging a careful reassessment of reported synthesis and biological activities associated with these compounds.
Assuntos
Solventes , Solventes/química , Humanos , Cinesinas/antagonistas & inibidores , Cinesinas/metabolismo , Estrutura Molecular , Simulação de Acoplamento Molecular , Cristalografia por Raios XRESUMO
The present work describes a complementary experimental and theoretical investigation of the spectroscopic properties of the four isostructural 3D Ln-MOFs (wherein PDC = pyrazole-3,5-dicarboxylate, [La2(PDC)3(H2O)4]·2H2O (1), [(La0.9Eu0.1)2(PDC)3(H2O)4]·2H2O (2), [(La0.9Tb0.1)2(PDC)3(H2O)4]·2H2O (3) and [(La0.9Eu0.5Tb0.5)2(PDC)3(H2O)4]·2H2O (4)). The experimental data and theoretical calculations show that the singular photophysical properties presented by these Ln-MOFs are induced by strong interaction between the Ln(3+) ions.
RESUMO
A modification of the conventional batch organosolv process is proposed in a way where the solid biomass remains inside a basket, physically separated from the liquid phase, with the vapor promoting the fractionation of the biomass and the extracted compounds and fragments being washed down to the liquid phase. The modified organosolv process applied to sugarcane bagasse (SB-M) delivers a rich cellulosic solid phase that after enzymatic hydrolysis leads to a hydrolyzed with approximately 100 g L-1 of glucose. At the same enzymatic hydrolysis conditions, the conventional organosolv process (SB-C) delivers a hydrolyzed with 80 g L-1 of glucose, while the autohydrolysis process (SB-A) leads to 55 g L-1 of glucose. These different results are related to the cellulose content: SB-M (70%), SB-C (57%), e SB-A (44%), as well the reduced lignin content in the SB-M. The novelty of this study is the confirmation that it is possible to degrade lignin from sugarcane bagasse and simultaneously remove its fragments from the cellulose fibers in a batch reactor containing an internal basket. This study describes a simple and rapid protocol for the isolation of the main components of lignocellulosic biomass (cellulose, hemicellulose, and lignin), which may lead to the study of new catalysts for the chemical transformation of these components separately or simultaneously to the step of pretreatment.
Assuntos
Celulose , Saccharum , Celulose/metabolismo , Lignina/metabolismo , Saccharum/química , Saccharum/metabolismo , Glucose/metabolismo , HidróliseRESUMO
New thiophene-dipicolinato-based compounds, K2nTdpa (n = 1, 2), were isolated. Their anions are sensitizers of lanthanide ion (LnIII) luminescence and singlet oxygen generation (1O2). Emission in the visible and near-infrared regions was observed for the LnIII complexes with efficiencies (ÏLn) ÏEu = 33% and ÏYb = 0.31% for 1Tdpa2- and ÏYb = 0.07% for 2Tdpa2-. The latter does not sensitize EuIII emission. Fluorescence imaging of HeLa live cells incubated with K3[Eu(1Tdpa)3] indicates that the complex permeates the cell membrane and localizes in the mitochondria. All complexes generate 1O2 in solution with efficiencies (ÏO12) as high as 13 and 23% for the GdIII complexes of 1Tdpa2- and 2Tdpa2-, respectively. [Ln(nTdpa)3]3- (n = 1, 2) are phototoxic to HeLa cells when irradiated with UV light with IC50 values as low as 4.2 µM for [Gd(2Tdpa)3]3- and 91.8 µM for [Eu(1Tdpa)3]3-. Flow cytometric analyses indicate both apoptotic and necrotic cell death pathways.