Conjugated Microporous Polymers with Built-In Magnetic Nanoparticles for Excellent Enrichment of Trace Hydroxylated Polycyclic Aromatic Hydrocarbons in Human Urine

Abstract

Conjugated microporous polymers (CMPs), linked by a covalent bond to form an extension of the aromatic ring skeleton, are microporous materials characterized by a highly conjugated structure and high stability. The present study reported on a novel strategy for the synthesis of CMPs with built-in magnetic nanoparticles for excellent enrichment of trace hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in human urine. We modified Fe3O4 nanoparticles with boronic acid groups and then reacted the nanoparticles with reactive monomers of polyphenylene conjugated microporous polymer (PP-CMP) to anchor the magnetic components in the PP-CMP framework. Chemical bonding between Fe3O4 nanoparticles and PP-CMP networks, together with equally firm covalent linkage and rigidity of the PP-CMP network, endows the magnetic PP-CMP with remarkable chemical stability and durability, even in harsh conditions. Magnetic PP-CMP has the characteristics of high conjugation ability, highly porous structure, and magnetism, which makes it an ideal magnetic adsorbent for trace analytes with aromatic conjugation structure. The adsorption mechanism of OH-PAHs on magnetic PP-CMP was investigated and demonstrated that hydrophobic interaction was important for the contribution of interaction between adsorbents and target analytes, together with the assistance of π-π stacking interaction. For the application, the magnetic PP-CMP was used for the enrichment of trace OH-PAHs in human urine of both smokers and nonsmokers in combination with high-performance liquid chromatography with fluorescence detection (HPLC-FLD). It showed good selectivity and excellent sensitivity to these OH-PAHs. Their detection limits were low and in the range of 0.01-0.08 μg·L(-1). The OH-PAHs were detected with different amounts from 0.054 to 0.802 μg·L(-1) in urine samples from smokers and nonsmokers. The recoveries were found to be 76.0%-107.8%. The results indicate that the magnetic PP-CMP offers an efficient enrichment method for trace OH-PAHs in human urine.

Aptamer‐Functionalized Magnetic Conjugated Organic Framework for Selective Extraction of Traces of Hydroxylated Polychlorinated Biphenyls in Human Serum

“…Fe 3 O 4 -150 acted as ac ore for the COF-Apt shell to form core-shell Fe 3 O 4 @COF-Apt-150 ( Figure 2B). [11] Fe 3 O 4 @COF-Apt-15w ith ac ore-shell structure was also obtained ( Figure 2D), and this indicated successful introductionoft he COF-Apts hell. [11] Fe 3 O 4 @COF-Apt-15w ith ac ore-shell structure was also obtained ( Figure 2D), and this indicated successful introductionoft he COF-Apts hell.…”

“…(2) and (3), respectively]: [11] Results were shown in Figure7.T he adsorption isotherm data of 2-OH-CB 124 were fitted with the Langmuir and Freundlich isotherm models[ Eqs.…”

“…[11] Then, as-synthesized Fe 3 O 4 particles (2.0 g) were dispersed in am ixture of ethanol (80 mL), H 2 O( 20 mL), and NH 3 ·H 2 O( 1.5 mL, 28 wt %), followed by the addition of TEOS (1.0 mL). [11] Then, as-synthesized Fe 3 O 4 particles (2.0 g) were dispersed in am ixture of ethanol (80 mL), H 2 O( 20 mL), and NH 3 ·H 2 O( 1.5 mL, 28 wt %), followed by the addition of TEOS (1.0 mL).…”

“…[4][5][6][7][8] Nevertheless, it is hard to extract them from the matrix due to their low density, which limits their furthera pplications in the area of separation and enrichment. [11] Magnetic nanoparticlesa re widely used in solid-phase extraction (SPE) due to their convenient and rapid separation from the sample solution with the help of am agnetic field. [11] Magnetic nanoparticlesa re widely used in solid-phase extraction (SPE) due to their convenient and rapid separation from the sample solution with the help of am agnetic field.…”

In Situ Growth of Flexible Polyphenylene-Conjugated Microporous Polymer Films for Fluorescence Detection of the Total Quantity of Developing Agents and Their Oxidation Products

“…The porosity of CMPs and its ability to bind specifically to target molecules indicate that this material could be used as a highly efficient separation and enrichment mediums [15]. Our group [16] has synthesized magnetic CMP nanoparticles for excellent enrichment of trace hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs). Due to adsorption effect of micropores for CMP and rapid separation of magnetic substance, magnetic CMP nanoparticles have been applied to concentrating trace OH-PAHs in human urine.…”