Ammonium N-(pyridin-2-ylmethyl)oxamate (AmPicOxam): A Novel Precursor of Calcium Oxalate Coating for Carbonate Stone Substrates.

Ammonium N-(pyridin-2-ylmethyl)oxamate (AmPicOxam), synthesized from O-methyl-N-(pyridin-2-ylmethyl)oxamate, was spectroscopically and structurally characterized and assayed as a novel precursor for the protection and consolidation of carbonate stone substrates. An in-depth characterization of treated and untreated biomicritic limestone and white Carrara marble samples was carried out by means of SEM microscopy, X-ray powder diffraction, helium pycnometry, determination of water transport properties, and pull-off tests. The improved solubility (1.00 M, 16.5% w/w) of the title compound with respect to ammonium oxalate (0.4 M, 5% w/w) results in the formation of a thicker protective coating of calcium oxalate (CaOx) dihydrate (weddellite) on marble and biomicrite samples after the treatment with 5% and 12% w/w water solutions, producing a reduction in the stone porosity and increased cohesion. Theoretical calculations were carried out at the DFT level to investigate both the electronic structure of the N-(pyridin-2-ylmethyl)oxamate anion and the hydrolysis reaction leading from AmPicOxam to CaOx.

Synthesis, characterization and DFT-modeling of novel agents for the protection and restoration of historical calcareous stone substrates.

The ammonium salts of oxamate (AmOxam) and monomethyloxalate (AmMeox), structurally related to ammonium oxalate (AmOx), were synthesized and characterized as protecting agents/filler for calcareous stone substrates. Both compounds featured an improved solubility in water and alcoholic-water mixtures with respect to AmOx. While AmOxam is stable in aqueous solution and reacts with calcite to afford the corresponding insoluble calcium oxamate (CaOxam), AmMeox spontaneously undergoes hydrolysis to give ammonium monohydrogen oxalate hemihydrate (AmBiox) and calcium oxalate (CaOx). Both compounds have been tested for the restoration of naturally weathered marble and biomicritic limestone. The formation of a superficial layer of CaOxam and CaOx was observed on stone samples treated with AmOxam and AmMeox, respectively, depending on the solvent mixture. A quantum-mechanical study was carried out at DFT level in order to investigate the nature of the interactions occurring between the lithic substrate (calcite) and the passivating agents, showing how the structural modifications on oxalic acid derivatives can be exploited to fine-tune their interaction with the calcite surface.