Search

This paper describes the poly(divinylbenzene) (PDVB) supported synthesis of quaternized hyperbranched macromolecules (QHMs) and its use as a highly selective, high-capacity mixed-mode anion-exchange (MAX) sorbent. In detail, the aminated PDVB support was firstly synthesized by copolymerization of divinylbenzene and 2-(diethylamino)ethyl methacrylate via Pickering emulsion polymerization. The QHMs were then grafted on PDVB by a divergent synthesis involving consecutive reactions of resorcinol diglycidyl ether with methylamine (N, N-dimethylethanolamine for terminal epoxides), which brought in a high density of quaternary ammonium functionalities. The changes of specific surface area (SBET), pore volume and ion exchange capacity (IEC) with generation number reveal that the QHMs have been grown successfully within the large meso-channels of the porous aminated PDVB. The best compromise between the SBET, pore volume and IEC was obtained at the 4th generation (G4). Due to the highest IEC (0.47 meq/g), the G4-QHMs was successfully applied for mixed-mode solid phase extraction (SPE) of acidic non-steroidal anti-inflammatory drugs (NSAIDs). An efficient approach based on the mixed-mode SPE coupled with HPLC-UV was developed for highly selective extraction and cleanup of nine NSAIDs (tolmetin, TLM; ketoprofen, KEP; naproxen, NAP; flurbiprofen, FLB; diclofenac, DIC; indomethacin, INM; ibuprofen, IBP; mefenamic acid, MFA; tolfenamic acid, TFA) in human urine samples. Under the optimized conditions, the method exhibited satisfactory recoveries ranging from 81.9% to 104.0% with relative standard deviation (RSD) values below 8.5%, good sensitivity (0.004–0.009 μg mL−1 limit of detection) and good linearity (coefficient of determination, R2 > 0.997, 0.01–0.2 μg mL−1 for NAP, 0.05–1.0 μg mL−1 for FLB, DIC, INM, MFA, TFA, 0.1–2.0 μg mL−1 for TLM, KEP, IBP). The hyperbranched MAX sorbent is superior to Oasis HLB and comparable to Oasis MAX in obtaining clean chromatographic profiles. Our results demonstrate the potential application of the hyperbranched MAX for complex sample analysis.

Iohexol (IHO), as one of iodinated X-ray contrast, is often used as not only a chemical marker for tracking wastewater contamination in aquatic environment, but also an ideal glomerular filtration rate marker for explorating kidney disease. To these aims, it is important to establish reliable, fast, and cheap methods to detect IHO in environmental and biological samples. This work describes for the first time the development of a selective, sensitive and reliable colorimetric sensing assay for the fast determination of IHO in environmental and biological samples based on 3-aminophenylboronic acid (3-APBA) mediated aggregation of gold nanoparticles (AuNPs). In this approach, 3-APBA can assemble on the AuNPs surface through electrostatic interaction between its amino groups with the negatively charged citrate stabilizer of AuNPs to form AuNP@3-APBA. Subsequently, the aggregation and visual color change of the assembled AuNP@3-APBA are induced by the covalent reaction between boronic acid ligands of 3-APBA and cis-diols of IHO. The developed assay presented a very simple operating procedure and a rapid analysis time of around 10 min. The developed assay also exhibited good selectivity and a low limit of detection (LOD) of 0.005 mM for detecting IHO. Moreover, the developed assay showed comparable accuracy and precision to the high-performance liquid chromatography-diode array detector (HPLC-DAD) method when used for the rapid determination of IHO in river water and human urine samples. The recoveries of IHO at three spiking levels were in the range of 91.5–106.3% with relative standard deviation (RSD) values below 6.39%.

Phthalates (PAEs) are a class of endocrine-disrupting chemicals. In recent years, the harmful effects of PAEs on human health, in particular their toxicity toward the reproductive system and development, have received significant attention because of their increasing production and usage. PAEs are ubiquitous in the environment and food products, resulting in unavoidable and long-term exposure in humans. Therefore, exposure and risk assessments of PAEs in humans are necessary. Screening and quantification of phthalate metabolites in urine is an important method for evaluating PAEs exposure, and establishing accurate analytical methods for this purpose has become a high priority. Phthalate monoesters and secondary metabolites are the most commonly targeted biomarkers of exposure to short-and long-chain PAEs, respectively. The combination of off-line or on-line solid phase extraction (SPE) with high performance liquid chromatography-tandem mass spectrometry has become the preferred method for the determination of phthalate metabolites. This paper reviews the analytical methods available for the detection of urinary phthalate metabolites and discusses the advantages, limitations, and challenges presented by each method in practical applications.

The dummy molecularly imprinted polymers were prepared by Pickering emulsion polymerization. 4,4'-(1-Phenylethylidene) bisphenol was selected as the dummy template to avoid the leakage of the target bisphenols. The microsphere particles were characterized by scanning electron microscopy and nitrogen adsorption-desorption measurements, demonstrating that the regular-shaped and medium-sized particles (40-70 μm) were obtained with a specific surface area of 355.759 m(2) /g and a total pore volume of 0.561 cm(3) /g. The molecular imprinting properties of the particles were evaluated by static adsorption and chromatographic evaluation experiments. The association constant and maximum adsorption amount of bisphenol A were 0.115 mmol/L and 3.327 μmol/g using Scatchard analysis. The microsphere particles were then used as a solid-phase extraction sorbent for selective extraction of seven bisphenols. The method of dummy molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography and diode array detection was successfully established for the extraction and determination of seven bisphenols from environmental sediment samples with method detection limits of 0.6-1.1 ng/g. Good recoveries (75.5-105.2%) for sediment samples at two spiking levels (500 and 250 ng/g) and reproducibility (RSDs < 7.7%, n = 3) were obtained.

A molecularly imprinted polymer (MIP) for highly selective solid-phase extraction (SPE) of bisphenol A (BPA) was prepared using phenolphthalein (PP) as the novel dummy template by bulk polymerization. A particle diameter distribution of 40&ndash, 60 &mu, m, a specific surface area of 359.8 m2&middot, g&minus, 1, and a total pore volume of 0.730 cm3&middot, 1 for the prepared PP-imprinted polymer (PPMIP) were obtained. Good selectivity and specific adsorption capacity for BPA of the prepared PPMIP were also demonstrated by the chromatographic evaluation and sorption experiments. The PPMIP as a SPE sorbent was evaluated for the selective extraction and clean-up of BPA from complex biological, environmental, and food samples. Meanwhile, an accurate and sensitive analytical method based on the PPMIP-SPE purification procedure coupled with high performance liquid chromatography-diode array detector (HPLC-DAD) detection has been successfully developed for the rapid determination of BPA from these samples, with detection limits of 1.3 ng&middot, mL&minus, 1 for bovine serum and milk, 2.6 ng&middot, 1 for human urine and edible oil, 5.2 ng&middot, 1 for soybean sauce, and 1.3 ng&middot, 1 for sediment. The BPA recoveries at two different spiking levels were in the range of 82.1&ndash, 106.9%, with relative standard deviation (RSD) values below 7.7%.

This work reports the preparation of molecularly imprinted polymer particles for the selective extraction and determination of four benzophenones from aqueous media. The polymer was prepared by using 4-vinylpridine as functional monomer, ethylene glycol dimethacrylate as cross-linker, acetonitrile as porogenic solvent and 2,2', 4,4'-tetrehydroxybenzophenone as template. Good specific adsorption capacity (Q(max) = 27.90 mu mol/g) for 2,2', 4,4'-tetrehydroxybenzophenone was obtained in the sorption experiment and good class selectivity for 2,2', 4,4'-tetrehydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dehydroxy-4,4'-dimethoxybenzophenone was demonstrated by the chromatographic evaluation experiment. Factors affecting the extraction efficiency of the molecularly imprinted solid-phase extraction procedure were investigated systematically. An accurate and sensitive analytical method based on the molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography and diode array detection has been successfully developed for the simultaneous determination of four benzophenones from tap water and river water with method detection limits of 0.25-0.72 ng/mL. The recoveries of benzophenones for water samples at two spiking levels (500 and 5000 ng/mL for each benzophenone) were in the range of 86.9-103.3% with relative standard deviations (n = 3) below 9.2%.

The bisphenol A (BPA) imprinted polymer microspheres were prepared by simple Pickering emulsion polymerization. Compared to traditional bulk polymerization, both high yields of polymer and good control of particle sizes were achieved. The characterization results of scanning electron microscopy and nitrogen adsorption-desorption measurements showed that the obtained molecularly imprinted polymer microsphere (MIPMS) particles possessed regular spherical shape, narrow diameter distribution (30-60 μm), a specific surface area (S(BET)) of 281.26 m(2) g(-1) and a total pore volume (V(t)) of 0.459 cm(3) g(-1). Good specific adsorption capacity for BPA was obtained in the sorption experiment and good class selectivity for BPA and its seven structural analogs (bisphenol F, bisphenol B, bisphenol E, bisphenol AF, bisphenol S, bisphenol AP and bisphenol Z) was demonstrated by the chromatographic evaluation experiment. The MIPMS as solid-phase extraction (SPE) packing material was then evaluated for extraction and clean-up of these bisphenols (BPs) from human urine samples. An accurate and sensitive analytical method based on the MIPMS-SPE coupled with HPLC-DAD has been successfully established for simultaneous determination of eight BPs from human urine samples with detection limits of 1.2-2.2 ng mL(-1). The recoveries of BPs for urine samples at two spiking levels (100 and 500 ng mL(-1) for each BP) were in the range of 81.3-106.7% with RSD values below 8.3%.

A new dendrimer-functionalized mesoporous silica material based on large-pore 3D cubic Korea Advanced Institute of Science and Technology-6 (KIT-6) was synthesized by the growing of dendritic branches inside the mesopores of aminopropyl functionalized KIT-6. Detailed physical characterizations using transmission electron microscopy, nitrogen adsorption-desorption measurements, Fourier transform infrared (FTIR) spectroscopy, and elemental analysis reveal that the multifunctional dendrimers have been grown successfully within the confined spaces of mesopores. Although the 3D ordered mesoporous architecture of KIT-6 was well preserved, there was a significant and continuous decrease in pore size, specific surface area (SBET) and pore volume when increasing dendrimer generation up to six. In order to get a compromise between the SBET, pore size and density of functionalities, the dendrimer-functionalized KIT-6 (DF-KIT-6) for generation 2 (SBET, 314.2 m(2) g(-1); pore size, 7.9 nm; carbon and nitrogen contents, 19.80% and 1.92%) was selected for solid phase extraction (SPE) applications. The DF-KIT-6 was then evaluated as a reversed-phase/anion-exchange mixed-mode sorbent for extraction of the selected acidic drugs (ketoprofen, KEP; naproxen, NAP; and ibuprofen, IBU), since the dendrimers contained both hydrocarbonaceous and amine functionalities. The effective parameters on extraction efficiency such as sample pH and volume, type and volume of eluent and wash solvents were optimized. Under the optimized experimental conditions, the DF-KIT-6 based SPE coupled with HPLC-UV method demonstrated good sensitivity (0.4-4.6 ng mL(-1) detection of limits) and linearity (R(2)>0.990 for 10-2000 ng mL(-1) of KEP and IBU, and 1-200 ng mL(-1) of NAP). The potential use of DF-KIT-6 sorbent for preconcentration and cleanup of acid drugs in human urine samples was also demonstrated. Satisfactory recoveries at two spiking levels (30 and 300 ng mL(-1) for KEP and IBU, 3 and 30 ng mL(-1) for NAP) were obtained in the range of 85.7-113.9% with RSD values below 9.3% (n=3).

The present work represents a simple and effective preparation of a novel mixed-mode anion-exchange (MAX) sorbent based on porous poly[2-(diethylamino)ethyl methacrylate-divinylbenzene] (poly(DEAEMA-DVB)) spherical particles synthesized by one-step Pickering emulsion polymerization. The poly(DEAEMA-DVB) particles were quaternized with 1,4-butanediol diglycidyl ether (BDDE) followed by triethylamine (TEA) via epoxy-amine reaction to offer strong anion exchange properties. The synthesized MAX sorbent was characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, nitrogen adsorption-desorption measurements and elemental analysis. The MAX sorbent possessed regular spherical shape and narrow diameter distribution (15–35 μm), a high IEC of 0.54 meq/g, with carbon and nitrogen contents of 80.3% and 1.62%, respectively. Compared to poly(DEAEMA-DVB), the MAX sorbent exhibited decreased SBET (390.5 vs. 515.3 m2 g−1), pore volume (0.74 vs. 0.85 cm3 g−1) and pore size (16.8 vs. 17.3 nm). Moreover, changes of N content for producing the MAX sorbent reveal a successful two-step quaternization, which can be highly related to such a high IEC. Finally, the MAX sorbent was successfully evaluated for selective isolation and purification of some selected acidic pharmaceuticals (ketoprofen, KEP; naproxen, NAP; and ibuprofen, IBP) from neutral (hydrocortisone, HYC), basic (carbamazepine, CAZ; amitriptyline, AMT) pharmaceuticals and other interferences in water samples using solid phase extraction (SPE). An efficient analytical method based on the MAX-based mixed-mode SPE coupled with HPLC-UV was developed for highly selective extraction and cleanup of acidic KEP, NAP and IBP in spiked wastewater samples. The developed method exhibited good sensitivity (0.009–0.085 μg L−1 limit of detection), satisfactory recoveries (82.1%–105.5%) and repeatabilities (relative standard deviation

A mesoporous silica Santa Barbara Amorphous-15 (SBA-15) has been first functionalized with 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (a silane with three amines) and then reacted with an excess of phenyl glycidyl ether to generate a mixed-mode anion-exchanger containing both anion-exchange (three amines) and reversed-phase (multiple ether-linked phenyls) functionalities in a single branched ligand. The resulting material has been characterized by scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, Fourier-transform infrared spectroscopy, and elemental analysis. The results obtained indicated a BET specific surface area (SBET) of 362.5m2g-1, a pore volume of 0.70cm3g-1 with a narrow pore size distribution centered at 6.6nm, and carbon and nitrogen contents of 28.30% and 2.84%, respectively. The dimensions of these particles (∼5μm diameter, ∼60μm length), their large surface areas, their high-density functionalities and anion-exchange mixed-mode characteristics make them very attractive for highly effective solid phase extraction (SPE) of acidic nonsteroidal anti-inflammatory drugs (NSAIDs). The important parameters on extraction efficiency including sample pH, breakthrough volume, type and volume of eluent were optimized. A simple and sensitive analytical method based on mixed-mode SPE coupled to high-performance liquid chromatography with ultraviolet detection (HPLC-UV) was developed and successfully applied to the analysis of four NSAIDs (ketoprofen, naproxen, diclofenac, and ibuprofen) in spiked real water samples with satisfactory recoveries (80.6-110.9%) and repeatability (relative standard deviation