Deterioration of Polyamideamine–Epichlorohydrin (PAE) in Aqueous Solutions During Storage: Structural Changes of PAE

Structural changes of polyamideamine–epichlorohydrin (PAE) in solution during storage at 4 °C and pH 4.2–4.5 for up to 8.9 years were studied by ¹H- and ¹³C-NMR analyses, colloidal titration and others. NMR signals due to 3-hydroxy-azetidinium groups of PAE decreased during storage, and correspondingly 2, 3-dihydroxypropyl groups were formed by the ring opening. The content of 3-hydroxy-azetidinium groups in PAE determined by ¹H-NMR were similar to that determined by the colloidal titration, although the former was higher than the latter. About 50% of the 3-hydroxy-azetidinium groups present in the fresh PAE were lost during storage for 8.9 years. Furthermore, ¹³C-NMR analysis revealed that significant depolymerization of polyamideamine chains occurred by hydrolysis of the amide linkages during storage. Rough evaluation of number average degree of polymerization (DPn) of the amideamine repeating unit showed that the DPn decreased from 12 to 2 during storage for 8.9 years.     

Oxygen Permeability and Biodegradability of Polyuronic Acids Prepared from Polysaccharides by TEMPO-Mediated Oxidation

Polyuronic acids, i.e., amylouronic acid, cellouronic acid and chitouronic acid, were prepared from starch, cellulose and chitin, respectively, by the 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-mediated oxidation, and their gas-barrier properties and biodegradability were studied in consideration to use the polyuronic acids as flexible packaging films or coating materials. Cellouronic acid and amylouronic acid had excellent oxygen-barrier properties similar to that of poly(vinyl alcohol) (PVA), while chitouronic acid did not. The regular chemical structures of the former two polyuronic acids with no bulky substituents or adducts may have brought about such high oxygen-barrier levels. An oxidized product prepared form fine microcrystalline cellulose by the TEMPO-mediated oxidation was not completely dissolved in water, but became a paste. However, this paste also formed sufficiently smooth films by coating, and had good gas-barrier property. All polyuronic acids prepared were biodegradable; cellouronic acid and chitouronic acid had high degrees of biodegradability, while amylouronic acid had quite low value. These various characteristics are significant for end use of these new polyuronic acids as gas-barrier materials for biodegradable packaging.     

Nitro-PAH exposures of occupationally-exposed traffic workers and associated urinary 1-nitropyrene metabolite concentrations

The assessment of occupational exposure to diesel exhaust(DE) is important from an epidemiological perspective. Urinary biomarkers of exposure have been proposed as a novel approach for measuring exposure to DE. In this study, we measured the concentrations of two urinary metabolites of 1-nitropyrene(1NP), a nitrated polycyclic aromatic hydrocarbon that has been suggested as a molecular marker of diesel particulate matter. These two metabolites, 6-hydroxy-1-nitropyrene and 8-hydroxy-1-nitropyrene, were determined in urine samples(10 m L) from a small group of workers who were occupationally-exposed to vehicle exhaust in Trujillo, Peru, before and after their workshifts. Workshift exposures to1 NP, as well as PM_(2.5), 2-nitropyrene and 2-nitrofluoranthene, were also measured.Exposures to 1NP were similar in all studied workers, averaging 105 ± 57.9 pg/m~3(±standard deviation). Median urinary concentrations of the average of the pre- and post-exposure samples for 6-hydroxy-1-nitropyrene and 8-hydroxy-1-nitropyrene, were found to be 3.9 and 2.3 pg metabolite/mg creatinine, respectively in the group of occupationally-exposed subjects(n = 17) studied. A direct relationship between workshift exposure to 1NP and urinary 1NP metabolites concentrations was not observed. However,the 1NP exposures and the creatinine-corrected urinary concentrations of the hydroxynitropyrene metabolites in these Peruvian traffic workers were similar to occupationally-exposed taxi drivers in Shenyang, China, and were higher than biomarker levels in office workers from Trujillo without occupational exposure to vehicle exhaust.This study provides further evidence that urinary metabolites of 1NP are associated with exposure to DE and may serve as a useful exposure biomarker.