Full-quantum mechanical fragment molecular orbital-based molecular dynamics (FMO-MD) simulations were applied to the hydration reaction of formaldehyde in water solution under neutral conditions. Two mechanisms, a concerted and a stepwise one, were considered with respect to the nucleophilic addition and the proton transfer. Preliminary molecular orbital calculations by means of polarized conti...

Reaction of titanium(IV) isopropoxide, Ti(OiPr)4, with an equimolar amount of phthalic anhydride resulted in the transfer of an isopropoxido group from the metal atom to one carbonyl group of the anhydride and coordination of the thus formed monoester to the titanium atom. One monoester ligand in Ti2(OiPr)6(μ2-OOC-C6H4-COOiPr)(η1-OOC-C6H4-COOiPr)(iPrOH) is bridging and the other is η1-coordinat...

Aldehyde and ketones are "carbonyl" derivatives of the hydrocarbons. A carbonyl is defined as an organic functional group consisting of a carbon atom involved in a double-bonding (pi) arrangement with oxygen. Recall that carbon has a valence of four and thus requires four electrons or bonds to achieve and octet. Oxygen has a valence of six and thus requires two electrons or bonds to satisfy its...

Pure rotational spectra of a prototypical prochiral ester, methyl benzoylformate (MBF), and the product of its enantioselective reduction, (R)-(-)-methyl mandelate (MM), were measured in the range of 5-16 GHz, using a cavity-based molecular beam Fourier-transform microwave spectrometer. Potential conformers were located using density functional theory calculations, and one conformer of each spe...

The DMSO reductase family consists of proteins that catalyze oxygen atom transfer reactions. These proteins are characterized by a mononuclear Mo center that is ligated by one or two molybdopterin cofactors (through the two thiolates). DMSO reductase itself is ligated by two molybdopterin cofactors and catalyzes the reduction of dimethyl sulfoxide to dimethyl sulfide. This reaction is important...

ion by the carbonyl oxygen atom of cytosine. This process may enable photoanomerisation and nucleobase loss, two previously unexplained photoreactions observed in pyrimidine nucleotides.

The nonenzymatic reaction between amino groups of proteins, lipids and nucleic acids with carbonyl group of reducing sugars is called glycation. Glycation primarily occurs at intrachain lysine residues of proteins and involves the condensation reaction of the carbonyl group of reducing sugar aldehydes with the amino groups of lysine residues. Several other carbonyl compounds bearing a reducing ...

Catalase is well-known as an antioxidant dismutating H2O2 to O2 and H2O. However, catalases evolved when metabolism was largely sulfur-based, long before O2 and reactive oxygen species (ROS) became abundant, suggesting catalase metabolizes reactive sulfide species (RSS). Here we examine catalase metabolism of H2Sn, the sulfur analog of H2O2, hydrogen sulfide (H2S) and other sulfur-bearing molec...