S-nitrosothiols and HS donors: Potential chemo-therapeutic agents in cancer.

Nitric Oxide (NO) and Hydrogen Sulfide (HS) are components of an "interactome", which is defined as a redox system involving the interactions of RSS, RNS and ROS. Chemical interaction by these species is common and is characterized by one and two electron oxidation, nitrosylation, nitration and sulfuration/polysulfidation reactions. NO and HS are gases that penetrate cell membranes, are synthesized by specific enzymes, are ubiquitous, regulate protein activities through post-translational modifications and participate in cell signaling.

Conformational study of the electronic interactions and nitric oxide release potential of new S‑nitrosothiols esters derivatives of ibuprofen, naproxen and phenyl acids substituted (SNO-ESTERS): Synthesis, infrared spectroscopy analysis and theoretical calculations.

The conformational study on the new S‑nitrosothiols esters (SNO-ESTERS): para-substituted (X = H, OMe, Cl and NO) S‑nitrosothiol derivatives 2‑methyl‑2‑(sulfanyl)propyl phenylacetates (R1), 2‑(4‑isobutylphenyl)propanoate (ibuprofen, R2), and 2‑(4‑isobutylphenyl)propanoate of 2‑methyl‑2‑(nitrososulfanyl)propyl (naproxen, R3) was performed using infrared spectroscopy (IR) in solvents with increasing polarity (CCl, CHCl, and CHCN), and theoretical calculations, to determine the preferential conformer and the potential of these compounds to release nitric oxide (NO). S‑Nitrosothiols were synthesized by esterification reactions, using chlorides of the corresponding carboxylic acids, with good yields (~60%). IR results showed that these compounds presented only one conformation, and the experimental data were supported by the theoretical results obtained by density functional theory (DFT) calculations using the 6311+G (2df, 2p) basis set.

Molecular Structures of Isomeric Ortho, Meta, and Para Bromo-Substituted α-Methylsulfonyl-α-diethoxyphosphoryl Acetophenones by X-ray and DFT Molecular Orbital Calculations.

The X-ray single crystal analysis of isomeric ortho, meta, and para bromo-substituted α-methylsulfonyl-α-diethoxyphosphoryl acetophenones showed that this class of compound adopts synclinal (gauche) conformations for both [-P(O)(OEt)2] and [-S(O)2Me] groups, with respect to the carbonyl functional group. The phosphonate, sulfonyl, and carbonyl functional groups are joined through an intramolecular network of attractive interactions, as detected by molecular orbital calculations at the M06-2X/6-31G(d,p) level. These interactions are responsible for the more stable conformations in the gas phase, which also persist in the solid-state structures.

Nitric oxide: Protein tyrosine phosphorylation and protein S-nitrosylation in cancer.

Cancer is a worldwide health problem leading to a high incidence of morbidity and mortality. Malignant transformation can occur by expression of oncogenes, over-expression and deregulated activation of proto-oncogenes, and inactivation of tumor suppressor genes. These cellular actions occur through stimulation of oncogenic signaling pathways.

1H and 13C NMR analysis of 2-acetamido-3-mercapto-3-methyl-N-aryl-butanamides and 2-acetamido-3-methyl-3-nitrososulfanyl-N-aryl-butanamide derivatives.

The complete assignment of the (1)H and (13)C NMR spectra of various 2-acetamido-3-mercapto-3-methyl-N-aryl-butanamides and 2-acetamide-3-methyl-3-nitrososulfanyl-N-aryl-butanamides with p-methoxy, o-chloro and m-chloro substituents is reported.

Complete assignment of 1H and 13C NMR spectra of alpha-phenylsulfinyl-N-methoxy-N-methylpropionamide and some p-substituted derivatives.

The complete assignment of the (1)H and (13)C NMR spectra of the diastereomeric pairs of some alpha-arylsulfinyl-substituted N-methoxy-N-methylpropionamides with the substituents methoxy, methyl, chloro, nitro is reported.

Complete assignment of 1H and 13C NMR spectra of some alpha-arylthio and alpha-arylsulfonyl substituted N-methoxy-N-methyl propionamides.

The complete assignments of the 1H and 13C NMR spectra of the some alpha-arylthio and alpha-arylsulfonyl substituted N-methoxy-N-methyl propionamides, bearing methoxy, methyl, chloro, and nitro as substituents at the phenyl ring are reported.

Substituent effects in the 13C NMR chemical shifts of alpha-mono-substituted acetonitriles.

13C chemical shifts empirical calculations, through a very simple additivity relationship, for the alpha-methylene carbon of some alpha-mono-substituted acetonitriles, Y-CH(2)-CN (Y=H, F, Cl, Br, I, OMe, OEt, SMe, SEt, NMe(2), NEt(2), Me and Et), lead to similar, or even better, results in comparison to the reported values obtained through Quantum Mechanics methods. The observed deviations, for some substituents, are very similar for both approaches. This divergence between experimental and calculated, either empirically or theoretically, values are smaller than for the corresponding acetones, amides, acetic acids and methyl esters, which had been named non-additivity effects (or intramolecular interaction chemical shifts, ICS) and attributed to some orbital interactions.

Complete assignment of 1H and 13C NMR spectra of some 4'-substituted diethyl 1-methylthio- and diethyl 1-methylsulfonyl-2-oxo-2-phenylethylphosphonates.

The complete assignment of 1H and 13C NMR spectra of some 4'-substituted diethyl 1-methylthio- and diethyl 1-methylsulfonyl-2-oxo-2-phenylethylphosphonates bearing as substituents methoxy, fluoro, chloro, bromo and nitro is reported.