Ethylenediamine-bound magnetite nanoparticles as dual function colorimetric sensor having charge transfer and nanozyme activity for TNT and tetryl detection.

A reusable, low-cost, and convenient ethylenediamine (EDA)-bound magnetite nanoparticles (MNPs)-based colorimetric sensor has been developed for dual function colorimetric determination of nitroaromatic explosives such as TNT and tetryl. Colorimetric detection of analytes may occur through two independent routes: (1) nano-Fe3O4- EDA- NH2 as σ-donor may interact with the σ- and π-acceptor aromatic-poly(NO2) groups to produce a colored charge-transfer (CT) complex; (2) nano-Fe3O4-EDA-NH2 as a Fenton-type nanozyme may generate reactive species that comprise hydroxyl radicals (•OH) with H2O2 to oxidize 3,3',5,5'-tetramethylbenzidine (TMB) to a blue-colored diimine (oxTMB-TMB) CT complex, where this color is bleached with TNT/tetryl because of donor-acceptor interactions between the explosive -NO2 groups and the -NH2 group of Fe3O4-EDA nanoparticles of restricted nanozyme activity. Both methods can quantify TNT well below the EPA recommended TNT residential screening level in soil, LOD being in the micromolar range. As EDA was covalently bound to MNPs, the same sensor can be separately reused six times for TNT and eight times for tetryl determination, using method (1). Common metal ions, anions, energetic materials, several camouflage materials, and soil components such as humates did not interfere with the nanosensor performance for TNT and tetryl. The combination of charge-transfer and nanozyme ability of Fe3O4- EDA-NH2 nanoparticles may bring a new approach to dual function colorimetric sensor design. To the best of our knowledge, this is the first dual function colorimetric sensor for TNT and tetryl using the same nanoparticles as sensing elements in two different detection systems involving either formation or bleaching of colored species. The proposed colorimetric sensor can determine nitroaromatic explosives in two different ways: method-1 for TNT and tetryl sensing with EDA-MNPs relies on the donor-acceptor interaction between the electron-deficient nitroaromatics and electron-rich amine groups covalently functionalized on MNPs to produce an absorbance at 512 nm. In method-2, EDA-MNPs having nanozyme activity react with H2O2 to form reactive species that can oxidize TMB to its blue-colored charge-transfer (CT) complex, where TNT and tetryl addition may partially inhibit the nanozyme activity of EDA-MNPs and cause color bleaching (decrement of 650 nm absorbance) by disrupting the CT complex formed from TMB. This is the first dual function colorimetric sensor for nitro explosives uniquely combining charge-transfer and nanozyme ability of EDA-Fe3O4 nanoparticles in the same nano-sensor.

Determination of total antioxidant capacity of Cynara Scolymus L. (globe artichoke) by using novel nanoparticle-based ferricyanide/Prussian blue assay.

A novel ferricyanide/Prussian blue (PB) assay for total antioxidant capacity (TAC) determination was developed exploiting the formation of PB nanoparticles in the presence of polyvinylpyrrolidone (PVP) as stabilizer. This improved method, named as "nanoparticle-based ferricyanide/Prussian blue assay (PBNP)", was applied to the TAC measurement of Cynara Scolymus L. (globe artichoke). The calibration results of the novel (PBNP) method were compared with those of a similar nanoparticle PB method performed in the absence of PVP, and of a sodium dodecyl sulfate-modified and acid-optimized ferricyanide reference assay. Compared to similar common Fe(III)-based TAC assays, much higher molar absorptivities, pointing out higher response to different kinds of antioxidants, were obtained with PBNP for all tested antioxidants, and lower LOD and LOQ values were achieved for thiols. As an additional advantage, methionine, not responding to other electron-transfer based TAC reagents, could be measured. PBNP could detect various antioxidants with one-two orders-of-magnitude lower LOD values than those of widely used TAC assays like CUPRAC and Folin-Ciocalteau well correlating with the proposed assay.

Modeling of copper(II) and lead(II) adsorption on kaolinite-based clay minerals individually and in the presence of humic acid.

The aim of this study is to explain how clay minerals adsorb heavy metals individually and in the presence of humic acid, and to model heavy metal adsorption specifically based on surface-metal binary and surface-metal-ligand ternary complexation. The adsorption of Cu(II) and Pb(II) on kaolinite-based clay minerals has been modeled by the aid of the FITEQL3.2 computer program using single- and double-site binding models of the Langmuir approach. Potentiometric titrations and adsorption capacity experiments were carried out in solutions containing different concentrations of the inert electrolyte NaClO4; however, the modeling of binary and ternary surface complexation was deliberately done at high ionic strength (0.1 M electrolyte) for eliminating adsorption onto the permanent negatively charged sites of kaolinite. A "two-site, two pKa" model was adapted, and as for the two surface sites responsible for adsorption, it may be arbitrarily assigned that [triple bond]S1OH sites represent silanol and organic functional groups such as carboxyl having pKa values close to that of silanol, and [triple bond]S2OH sites represent aluminol and organic functional groups such as phenolics whose pKa values are close to that of aluminol, as all the studied clays contained organic carbon. Copper(II) showed a higher adsorption capacity and higher binding constants, while lead(II), being a softer cation (in respect to HSAB theory) preferred the softer basic sites with aluminol-phenol functional groups. Heavy metal cations are assumed to bind to the clay surface as the sole (unhydrolyzed) M(II) ion and form monodentate surface complexes. Cu(II) and Pb(II) adsorption in the presence of humic acid was modeled using a double-site binding model by the aid of FITEQL3.2, and then the whole system including binary surface-metal and surface-ligand and ternary surface-metal-ligand complexes was resolved with respect to species distributions and relevant stability constants. Electrostatic effects were accounted for using a diffuse layer model (DLM) requiring minimum number of adjustable parameters. Metal adsorption onto clay at low pH increased in the presence of humic acid, and the metal adsorption vs pH curves of metal-kaolinite-humic acid suspensions were much steeper (and distinctly S shaped) compared to the wider pH-gradient curves observed in binary clay-metal systems. The clay mineral in the presence of humic acid probably behaved more like a chelating ion-exchanger sorbent for heavy metals rather than being a simple inorganic ion exchanger.

Determination of total antioxidant capacity of humic acids using CUPRAC, Folin-Ciocalteu, noble metal nanoparticle- and solid-liquid extraction-based methods.

Total antioxidant capacity (TAC) of humic acid (HA) samples was determined using CUPRAC (CUPric Reducing Antioxidant Capacity), FC (Folin-Ciocalteu), QUENCHER-CUPRAC, QUENCHER-FC, Ag-NP (Silver nanoparticle)‒ and Au-NP (Gold nanoparticle)‒based methods. Conventional FC and modified FC (MFC) methods were applied to solid samples. Because of decreased solubility of Folin-Ciocalteu's phenol reagent in organic solvents, solvent effect on TAC measurement was investigated using QUENCHER-CUPRAC assay by using ethanol:distilled water and dimethyl sulfoxide:distilled water with varying ratios. To see the combined effect of solubilization (leaching) and TAC measurement of humic acids simultaneously, QUENCHER experiments were performed at 25°C and 50°C; QUENCHER-CUPRAC and QUENCHER-FC methods agreed well and had similar precision in F-statistics. Although the Gibbs free energy change (ΔG°) of the oxidation of HA dihydroxy phenols with the test reagents were negative, the ΔG° was positive only for the reaction of CUPRAC reagent with isolated monohydric phenols, showing CUPRAC selectivity toward polyphenolic antioxidants. This is the first work on the antioxidant capacity measurement of HA having a sparingly soluble matrix where enhanced solubilization of bound phenolics is achieved with coupled oxidation by TAC reagents.