Facile Synthesis of Polysulfoaminoanthraquinone Nanosorbents for Rapid Removal and Ultrasensitive Fluorescent Detection of Heavy Metal Ions

Abstract

Poly(5-sulfo-1-aminoanthraquinone) nanoparticles were facilely synthesized by a chemical oxidative polymerization of 5-sulfo-1-aminoanthraquinone. The polymerization parameters such as oxidant species, acid species, acid concentration, oxidant/monomer ratio, polymerization time, and temperature were systematically studied to significantly optimize the synthetic yield, structure, and multifunctionalities of the target nanoparticles. The molecular structure, size distribution, morphology, and properties of the nanoparticles were detailedly analyzed by IR, UV-vis, and fluorescence spectroscopies, element analyses, MALDI-MS, X-ray diffraction, FESEM, AFM, laser particle analyzer, and simultaneous TG/ DSC. It is found that K 2 CrO 4 oxidant and aqueous HClO 4 without any external stabilizers are an optimal combination for synthesizing the nanoparticles with a clean surface, large πconjugation, narrow size distribution, intrinsic semiconductivity, blue fluorescence, and inherent self-stability that is ascribed to many negatively charged sulfonic groups on their macromolecular chains. In particular, the nanoparticles having a unique synergic combination of five kinds of active -NH-, -Nd, -NH 2 , dO, and -SO 3 H groups with an appropriate specific area of 115.15 m 2 g -1 exhibit very high removal percentage of respective lead and mercury of 99.6 and 99.8% at initial concentrations of even up to 200 mg L -1 , ultrarapid initial adsorption rate of up to 10350 (Pb(II)) and 14140 (Hg(II)) mg g -1 h -1 , increased adsorbability order of Zn(II) < Fe(III) < Cu(II) , Ag(I) < Cd(II) < Pb(II) < Hg(II), and satisfactory removal of harmful heavy metal ions from ambient wastewaters, becoming ultrarapid chelate nanosorbents. Furthermore, PSA solution could be served as an advanced fluorescent chemosensor having ultrahigh sensitivity and high selectivity toward Pb(II) because of its very superior detection limit down to 1.0 Â 10 -10 M and strong anti-interference to almost all other metal ions.

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“…This means an increased extension of the conjugation structure along the molecular chains. [31] Note that the UV-visible spectral characteristics in Figure 3 a reveal a regular variation of the p-conjugated structures of the P15DAN nanospheres with the dispersion medium from NMP to THF, ethanol, and water, which indicates different interaction between the nanospheres and the dispersants. Notably, the addition of Cu II results in a drastic UV-visible spectral change (see Figure 3 b).…”

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“…In other words, the fabricated sensor is highly selective for assessment of MB in real samples containing dyes or other ions. [30,31] and potentiometry based [32] sensors with ultrasensitive nature.…”

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“…The absorption bands between 370 and 430 nm are ascribed to π–π* transitions in the phenazine ring conjugated to the two lone pairs of nitrogen of the NH 2 groups (phenazine has an absorbance at 364 nm). The absorption bands in the range 260 − 280 nm are due to π–π* transitions of the benzenoid and quinonoid structures . However, two small additional absorption bands at 590 and 640 nm in the P(tBu‐ o PD) polymer (Fig.…”