A large effort is being made to develop nanosorbents with tunable surface chemistry for enhanced adsorption affinity and selectivity toward target organic contaminants. Heteroatom N-doped multiwall carbon nanotubes (N-MCNT) were synthesized by chemical vapor deposition of pyridine and were further investigated for the adsorptive removal of several aromatic chemicals varying in electronic donor and acceptor ability from aqueous solutions using a batch technique. Compared with commercial nondoped multiwall carbon nanotubes (MCNT), N-MCNT had similar specific surface area, morphology, and pore-size distribution but more hydrophilic surfaces and more surface defects due to the doping of graphitic and pyridinic N atoms. N-MCNT exhibited enhanced adsorption (2-10 folds) for the π-donor chemicals (2-naphthol and 1-naphthalmine) at pH ∼6 but similar adsorption for the weak π-donor chemical (naphthalene) and even lower adsorption (up to a 2-fold change) for the π-acceptor chemical (1,3-dinitrobenzene). The enhanced adsorption of 2-naphthol and 1-naphthalmine to N-MCNT was mainly attributed to the favored π-π electron-donor-acceptor (EDA) interaction between the π-donor adsorbate molecule and the polarized N-heterocyclic aromatic ring (π-acceptor) on N-MCNT. The proposed adsorption enhancement mechanisms were further tested through the pH effects on adsorption and the density function theory (DFT) calculation. The results show for the first time that the adsorptive interaction of π-donor aromatic compounds with carbon nanomaterials can be facilitated by N-doping.
Although
the distribution of progestagens in aquatic environments
has been widely reported, details on their uptake, elimination, and
biotransformation in fish have received little attention. This study
investigated the uptake, elimination, and biotransformation potential
of a progestagen, cyproterone acetate (CPTA), in Nile tilapia (Oreochromis niloticus) exposed to an environmentally relevant
concentration under semistatic regimes. CPTA in tilapia tissues followed
a similar pattern, reaching a concentration plateau within 4 days
of exposure, and dropping to below limits of quantitation within 4
days of elimination. The calculated steady-state bioconcentration
factors suggest a low bioconcentration potential of CPTA in juvenile
tilapia. Results of enzymatic hydrolysis treatments revealed that
no conjugates of CPTA were present in tissues, but conjugated biotransformation
products of CPTA were found in bile, liver, and muscle. Most CPTA
entered tissues and then was biotransformed into seven different products
by phase I and phase II metabolism. The concentrations of endogenous
cortisol were significantly influenced by CPTA in plasma and liver
during the uptake period. These findings suggest that biotransformation
products of CPTA should be considered for the assessment of the bioconcentration
potential and ecological effects of progestagens.
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