Unveiling the mechanisms behind the chemical vapor generation of plumbane for trace analysis of lead.

The mechanisms controlling the generation of PbH4 by reaction of inorganic Pb(II) with aqueous NaBH4 were investigated both in the presence and in the absence of the additive K3Fe(CN)6. For the first time PbH4 has been identified in analytical chemical vapor generation (CVG) by using gas chromatographic mass spectrometry (GC-MS), which allows the use of deuterium labelled experiments. In the absence of the additive, under reaction conditions typically employed for trace lead determination by CVG, Pb(II) is converted to solid species and no volatile lead species can be detected by either atomic or mass spectrometry for Pb(II) concentration up to 100 mg L-1. In alkaline conditions Pb(II) substrates are unreactive towards NaBH4. In the presence of K3Fe(CN)6, deuterium labelled experiments clearly indicated that the generated PbH4 is formed by the direct transfer of hydride from borane to lead atoms. Kinetic experiments were carried out to evaluate the rate of reduction of K3Fe(CN)6 by NaBH4, the rate of hydrolysis of NaBH4 both in the presence and in the absence of K3Fe(CN)6, and the rate of dihydrogen evolution following NaBH4 hydrolysis. The effect of delayed addition of Pb(II) to NaBH4-HCl- K3Fe(CN)6, and K3Fe(CN)6 to NaBH4-HCl-Pb(II) reaction mixtures on the efficiency of plumbane generation was investigated by continuous flow CVG coupled with atomic fluorescence spectrometry. The collected evidences, complemented with thermodynamic considerations and literature data, have made it possible to clarify long-standing controversial aspects related to the mechanism of plumbane generation and the role of K3Fe(CN)6 additive.

Binding of model polycyclic aromatic hydrocarbons and carbamate-pesticides to DNA, BSA, micelles and liposomes.

The binding to biosubstrates and micellar systems of pollutants as the polycyclic aromatic hydrocarbon (PAH) derivatives 1-aminopyrene (1-PyNH2) and 1-hydroxymethylpyrene (1-PyMeOH) and the carbamate-pesticides 1-naphthyl-N-methylcarbamate (carbaryl, CA) and methyl benzimidazol-2-ylcarbamate (carbendazim, CBZ) was analysed through an integrated strategy combining spectroscopy and quantum chemistry. As biosubstrates, natural DNA and bovine serum albumin (BSA) were taken into account for a thermodynamic analysis of the binding features through spectrophotometric and spectrofluorometric techniques. In all cases, a strong DNA interaction is present and intercalation is supposed as the major binding mode. For the PAH derivatives, DNA binding is found to be favoured under high salt conditions and BSA static quenching and binding with 1:1 stoichiometry occurs. The molecular structure and optical properties of 1-PyNH2, CA and CBZ together with their intercalated adducts in DNA were studied also by means of quantum chemical approach. The (TD)DFT calculations on intercalated dye/DNA adducts quantitatively reproduce the experimentally observed spectroscopic changes, thus confirming the intercalation hypothesis. The theoretical approach also provides information on the adducts' geometries and on the amount of charge transfer with DNA. Moreover, ultrafiltration tests in the presence of anionic (SDS), cationic (DTAC) and neutral (Triton X) micellar aggregates and liposomes provided insights into lipophilicity and cellular membrane affinity. PAH derivatives show high retention coefficient in all cases, whereas in the case of carbamate-pesticides micellar retention might be significantly reduced and is very limited in the case of liposomes.