title: Towards the design of organocatalysts for nerve agents remediation: The case of the active hydrolysis of DCNP (a Tabun mimic) catalyzed by simple amine-containing derivatives.
abstract: We report herein a study of the hydrolysis of Tabun mimic DCNP in the presence of different amines, aminoalcohols and glycols as potential suitable organocatalysts for DCNP degradation. Experiments were performed in CD3CN in the presence of 5% D2O, which is a suitable solvent mixture to follow the DCNP hydrolysis. These studies allowed the definition of different DCNP depletion paths, resulting in the formation of diethylphosphoric acid, tetraethylpyrophosphate and phosphoramide species as final products. Without organocatalysts, DCNP hydrolysis occurred mainly via an autocatalysis path. Addition of tertiary amines in sub-stoichiometric amounts largely enhanced DCNP depletion whereas non-tertiary polyamines reacted even faster. Glycols induced very slight increment in the DCNP hydrolysis, whereas DCNP hydrolysis increased sharply in the presence of certain aminoalcohols especially, 2-(2-aminoethylamino)ethanol. For the latter compound, DCNP depletion occurred ca. 80-fold faster than in the absence of organocatalysts. The kinetic studies revealed that DCNP hydrolysis in the presence of 2-(2-aminoethylamino)ethanol occurred via a catalytic process, in which the aminoalcohol was involved. DCNP hydrolysis generally depended strongly on the structure of the amine, and it was found that the presence of the OHCH2CH2N moiety in the organocatalyst structure seems important to induce a fast degradation of DCNP.
authors.affiliation: Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universidad Politécnica de Valencia-Universidad de Valencia, Spain; Departamento de Química, Universidad Politécnica de Valencia, Camino de Vera s/n, 46022 Valencia, Spain; CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BNN), Spain.
authors.forename: Andrea
authors.initials: A
authors.lastname: Barba-Bon
authors.affiliation: Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universidad Politécnica de Valencia-Universidad de Valencia, Spain; Departamento de Química, Universidad Politécnica de Valencia, Camino de Vera s/n, 46022 Valencia, Spain; CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BNN), Spain.
authors.forename: Ramón
authors.initials: R
authors.lastname: Martínez-Máñez
authors.affiliation: Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universidad Politécnica de Valencia-Universidad de Valencia, Spain; Departamento de Química, Universidad Politécnica de Valencia, Camino de Vera s/n, 46022 Valencia, Spain; CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BNN), Spain.
authors.forename: Félix
authors.initials: F
authors.lastname: Sancenón
authors.affiliation: Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universidad Politécnica de Valencia-Universidad de Valencia, Spain; Departamento de Química Orgánica, Universitat de València, Dr. Moliner 50, 46100 Burjassot, Valencia, Spain. Electronic address: ana.costero@uv.es.
authors.forename: Ana M
authors.initials: AM
authors.lastname: Costero
authors.affiliation: Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universidad Politécnica de Valencia-Universidad de Valencia, Spain; Departamento de Química Orgánica, Universitat de València, Dr. Moliner 50, 46100 Burjassot, Valencia, Spain.
authors.forename: Salvador
authors.initials: S
authors.lastname: Gil
authors.affiliation: Institut de Cíencia dels Materials (ICMUV), c/ Catedrtico Beltrán 2, 46980 Valencia, Spain. Electronic address: francisco.perez@uv.es.
authors.forename: Francisco
authors.initials: F
authors.lastname: Pérez-Pla
authors.affiliation: Institut de Cíencia dels Materials (ICMUV), c/ Catedrtico Beltrán 2, 46980 Valencia, Spain.
authors.forename: Elisa
authors.initials: E
authors.lastname: Llopis
mesh_terms: D000588:Amines / Q000737:chemistry*; D000605:Amino Alcohols / Q000737:chemistry; D002384:Catalysis; D002619:Chemical Warfare Agents / Q000737:chemistry / Q000633:toxicity*; D052918:Environmental Restoration and Remediation / Q000379:methods*; D006018:Glycols / Q000737:chemistry; D006868:Hydrolysis; D007700:Kinetics; D000067397:Nerve Agents / Q000737:chemistry / Q000633:toxicity*; D009596:Nitrophenols / Q000737:chemistry / Q000633:toxicity*; D010755:Organophosphates / Q000737:chemistry / Q000633:toxicity*
chemical_list: D000588:Amines; D000605:Amino Alcohols; D002619:Chemical Warfare Agents; D006018:Glycols; D000067397:Nerve Agents; D009596:Nitrophenols; D010755:Organophosphates; C015802:2,6-dichloro-4-nitrophenol; C009374:tabun
keywords: Diethylcyanophosphonate; Hydrolysis; Kinetics; Nerve agent simulant; Organocatalysts