Wenhui Lu

Highly Sensitive and Selective Colorimetric Sensing of Hg2+ Based on the Morphology Transition of Silver Nanoprisms

A simple colorimetric approach for mercury ion (Hg(2+)) sensing was developed that was based on the Hg(2+)-induced deprotection and morphology transition of 1-dodecanethiol (C(12)H(25)SH)-capped silver nanoprisms (Ag NPRs) upon the presence of iodides at room temperature. The abstraction of C(12)H(25)SH from the surface of Ag NPRs by Hg(2+) led to their deprotection of Ag NPRs and the formation of complexation between silver ions and excess iodide ions. Also, the silver atoms were consumed and moved from the surface of Ag NPRs, accompanying the changes in the particle morphology that resulted in a change of color and UV-vis absorption spectra of the colloidal solution. With increasing concentrations of Hg(2+) from 10 to 500 nM, the surface plasma resonance spectral band of Ag NPRs emerged as a blue shift and exhibited a good linear relationship, and the limit of detection was 3.3 nM. Furthermore, the developed method was applied for detecting Hg(2+) in different real water samples with satisfying recoveries over 92%.

Recent Advances in Dispersive Liquid-Liquid Microextraction for Organic Compounds Analysis in Environmental Water: A Review

Dispersive liquid-liquid microextraction (DLLME) is a novel microextraction technique with a great potential in sample pretreatment, which has been increasingly used for preconcentration of diverse analytes. This review updates the state of the art and discusses promising prospects of DLLME, especially focuses on its combined use with chromatographic techniques for organic compounds analysis in environmental water samples. General and specific concepts of the fundamental theory of DLLME are described, and examples of recent innovations and applications are provided to demonstrate its potential for the determination of a wide range of organic compounds in various water matrices. Moreover, some limitations related to DLLME are also discussed in detail, and an outlook on the future of the technique, specifically its coupling with other pretreatment approaches, separation and detection techniques, is also given.

Water-compatible temperature and magnetic dual-responsive molecularly imprinted polymers for recognition and extraction of bisphenol A

Versatile molecularly imprinted polymers (MIPs) have been widely applied to various sample matrices, however, molecular recognition in aqueous media is still difficult. Stimuli-responsive MIPs have received increasing attentions due to their unique feature that the molecular recognition is regulated by specific external stimuli. Herein, water-compatible temperature and magnetic dual-responsive MIPs (WC-TMMIPs) with hydrophilic brushes were prepared via reversible addition-fragmentation chain transfer precipitation polymerization for reversible and selective recognition and extraction of bisphenol A (BPA). Transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FT-IR) and vibrating sample magnetometry (VSM) as characterization methods were used to examine the successful synthesis of polymers, and the resultant WC-TMMIPs showed excellent thermosensitivity and simple rapid magnetic separation. Controlled adsorption and release of BPA by temperature regulation were investigated systematically, and the maximum adsorption and removal efficiency toward BPA in aqueous solutions were attained at 35 °C and 45 °C, respectively, as well as a good recoverability was exhibited with the precision less than 5% through five adsorption-desorption cycles. Phenolic structural analogs were tested and good recognition specificity for BPA was displayed. Accordingly, the WC-TMMIPs were employed as adsorbents for magnetic solid-phase extraction (MSPE) and packed SPE of BPA from seawater samples. Using the two modes followed by HPLC-UV determination, excellent linearity was attained in the range of 0.1-14.5 μM and 1.3-125 nM, with low detection limits of 0.02 μM and 0.18 nM, respectively. Satisfactory recoveries for spiked seawater samples were achieved ranging from 86.3-103.5% and 96.2-104.3% with RSD within 2.12-4.33%. The intelligent WC-TMMIPs combining water-compatibility, molecular recognition, magnetic separation, and temperature regulation proved potentially applicable for selective identification, controlled adsorption/release and high-efficiency enrichment/removal of trace targets in complicated aqueous media.

Metal organic frameworks (MOFs) for magnetic solid-phase extraction of pyrazole/pyrrole pesticides in environmental water samples followed by HPLC-DAD determination

Magnetic metal-organic frameworks (MOFs, [MIL-101]) were prepared and used as magnetic solid-phase extraction (MSPE) adsorbents for preconcentration of four kinds of pyrazole/pyrrole pesticides (flusilazole, fipronil, chlorfenapyr, and fenpyroximate) in environmental water samples, followed by high-performance liquid chromatography-diode-array detector (HPLC-DAD) determination. Several variables affecting MSPE efficiency were systematically investigated, including amount of MIL-101, extraction time, sample pH, salt concentration, type of desorption solvent and desorption number of times. Under optimized conditions, excellent linearity was achieved in the range of 5.0-200.0μg/L for flusilazole and fipronil, and 2.0-200.0μg/L for chlorfenapyr and fenpyroximate, with correlation coefficients r>0.9911. Limits of detection and quantification were 0.3-1.5μg/L and 1.0-5.0μg/L, respectively. The intra-day and inter-day precision (relative standard deviation, n=6, %) at three spiked levels were 1.1-5.4% and 3.9-7.8% in terms of peak area, respectively. The method recoveries at three fortified concentration levels ranged from 81.8% to 107.5% for reservoir water samples, 81.0-99.5% for river water samples, and 80.2-106.5% for seawater samples. The developed MOFs based MSPE coupled with HPLC method proved to be a convenient, rapid and eco-friendly alternative to the sensitive determination of pyrazole/pyrrole pesticides with high repeatability and excellent practical applicability.

Determination of six sulfonylurea herbicides in environmental water samples by magnetic solid-phase extraction using multi-walled carbon nanotubes as adsorbents coupled with high-performance liquid chromatography

Magnetic solid-phase extraction (MSPE) using magnetic multi-walled carbon nanotubes (mag-MWCNTs) as adsorbents, coupled with high-performance liquid chromatography-diode-array detector (HPLC-DAD), was developed for the simultaneous separation and determination of six types of sulfonylurea herbicides (SUs) in environmental water samples. Several variables affecting MSPE efficiency were systematically investigated, including the type and volume of desorption solvent, sample solution pH, salt concentration, amount of mag-MWCNTs, and extraction and desorption time. Response surface was employed to assist in the MSPE optimization. Under optimized conditions, excellent linearity was achieved in the range of 0.05-5.0μg/L for all six SUs, with coefficients of correlation r>0.9994, and preconcentration factors ranging from 178 to 210. Limits of detection and quantification were 0.01-0.04μg/L and 0.03-0.13μg/L, respectively. The intra-day and inter-day precision (relative standard deviations, n=6, %) at three spiked levels were 2.0-11.0% and 2.1-12.9% in terms of peak area, respectively. The method recoveries at three fortified concentrations were obtained within 76.7-106.9% for reservoir water samples and 78.2-105.4% for tap water samples. The developed MSPE-HPLC method demonstrated high sensitivity, repeatability, simplicity, rapidity, and excellent practical applicability.

Thermosensitive molecularly imprinted polymers on porous carriers: Preparation, characterization and properties as novel adsorbents for bisphenol A

Thermosensitive molecularly imprinted polymers (T-MIPs) on porous carriers were prepared via the synergy of dual functional monomers of 4-vinylpyridine (VP) and N-isopropylacrylamide (NIPAM), for selective recognition and controlled adsorption and release of bisphenol A (BPA) by the temperature regulation. The porous polymer supporter was synthesized by multistep swelling of polystyrene and then both the NIPAM with temperature responsiveness and the basic monomers of VP were grafted on them in a simple way. The resultant T-MIPs showed high binding capacity, fast kinetics, and the adsorption processes were found to follow Langmuir-Freundlich isotherm and pseudo-second-order kinetic models. The adsorption capacity increased slightly along with the rise of temperature (such as 20°C) under lower critical solution temperature (LCST, 33°C) and decreased fast above LCST (such as 50°C). Subsequently, the T-MIPs were employed as novel adsorbents for selective solid-phase extraction (SPE) of BPA from seawater and yogurt samples. Satisfying recoveries in the range of 94.83-98.47% were obtained with the precision of 3.21% at ambient temperature (20°C). Through 6 adsorption-desorption cycles, the reusable T-MIPs exhibited a good recoverability with the relative standard error within 9.8%. The smart T-MIPs provided great potentials for selective identification, adsorption/release and removal of BPA by simple stimuli responsive regulation.

Speciation analysis of mercury in water samples by dispersive liquid–liquid microextraction coupled to capillary electrophoresis

In this study, a method of pretreatment and speciation analysis of mercury by dispersive liquid–liquid microextraction along with CE was developed. The method was based on the fact that mercury species including methylmercury (MeHg), ethylmercury (EtHg), phenylmercury (PhHg), and Hg(II) were complexed with 1‐(2‐pyridylazo)‐2‐naphthol to form hydrophobic chelates and l‐cysteine could displace 1‐(2‐pyridylazo)‐2‐naphthol to form hydrophilic chelates with the four mercury species. Factors affecting complex formation and extraction efficiency, such as pH value, type, and volume of extractive solvent and disperser solvent, concentration of the chelating agent, ultrasonic time, and buffer solution were investigated. Under the optimal conditions, the enrichment factors were 102, 118, 547, and 46, and the LODs were 1.79, 1.62, 0.23, and 1.50 μg/L for MeHg, EtHg, PhHg, and Hg(II), respectively. Method precisions (RSD, n = 5) were in the range of 0.29–0.54% for migration time, and 3.08–7.80% for peak area. Satisfactory recoveries ranging from 82.38 to 98.76% were obtained with seawater, lake, and tap water samples spiked at three concentration levels, respectively, with RSD (n = 5) of 1.98–7.18%. This method was demonstrated to be simple, convenient, rapid, cost‐effective, and environmentally benign, and could be used as an ideal alternative to existing methods for analyzing trace residues of mercury species in water samples.

One-pot synthesis of magnetic iron oxide nanoparticle-multiwalled carbon nanotube composites for enhanced removal of Cr(VI) from aqueous solution

Magnetic nanoparticle-multiwalled carbon nanotubes composites (MNP/MWCNTs) were prepared using 1,6-hexanediamine functionalized Fe3O4 nanoparticles (MNP) linked to carboxylic MWCNTs by facile one-pot solvothermal synthesis for highly efficient removal of Cr(VI) from aqueous solution. The easily obtained magnetic nanocomposites were systematically characterized, and several major factors affecting the adsorption-based removal were investigated, including solution pH, adsorbent dosage, temperature and contact time. The removal efficiency was highly dependent on solution pH; low pH facilitated removal with the maximum efficiency at pH 2.0. The adsorption isotherm was well fitted with the Langmuir isotherm model and the adsorption capacity increased with the temperature increasing. The adsorption kinetic data could be well described by the pseudo-second-order and the intraparticle diffusion models, indicating that the intraparticle diffusion was not the only rate-limiting step. The MNP/MWCNTs displayed excellent selectivity and high anti-interference ability toward Cr(VI) when confronted with commonly coexisting ions. By using an external magnetic field, the exhausted MNP/MWCNTs could be readily separated from the solution after adsorption of Cr(VI) and well regenerated, and could keep about 80% removal efficiency in the fifth adsorption-desorption cycle. The simple, rapid and reliable MNP/MWCNT-based method proved to be a cost-effective, convenient and potentially applicable way to targeted pollutant removal and wastewater treatment.

Headspace solid-phase microextraction with on-fiber derivatization for the determination of aldehydes in algae by gas chromatography–mass spectrometry

A simple, fast, sensitive and cost-effective method based on headspace solid-phase microextraction (HS-SPME) with on-fiber derivatization coupled with gas chromatography-mass spectrometry was developed for the determination of six typical aldehydes, 2E-hexenal, heptanal, 2E-heptenal, 2E,4E-heptadienal, 2E-decenal and 2E,4E-decadienal in laboratory algae cultures. As derivatization reagent, O-2,3,4,5,6-(pentafluorobenzyl) hydroxylamine hydrochloride, was loaded onto the poly(dimethylsiloxane)/divinylbenzene fiber for aldehydes on-fiber derivatization prior to HS-SPME. Various influence factors of extraction efficiency were systematically investigated. Under optimized extraction conditions, excellent method performances for all the six aldehydes were attained, such as satisfactory extraction recoveries ranging from 67.1 to 117%, with the precision (relative standard deviation) within 5.3-11.1%, and low detection limits in the range of 0.026-0.044 μg/L. The validated method was successfully applied for the analysis of the aldehydes in two diatoms (Skeletonema costatum and Chaetoceros muelleri), two pyrrophytas (Prorocentrum micans and Scrippsiella trochoidea) and Calanus sinicus eggs (feeding on the two diatoms above).

Multi-template imprinted polymers for simultaneous selective solid-phase extraction of six phenolic compounds in water samples followed by determination using capillary electrophoresis

Novel multi-template molecularly imprinted polymers (mt-MIPs) with six phenolic compounds as the template, namely phenol, 4-chlorophenol (4-CP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,4-dichlorophenol (2,4-DCP), 2-chlorophenol (2-CP) and 2,6-dichlorophenol (2,6-DCP), were prepared by precipitation polymerization and used as the adsorbents of solid-phase extraction (SPE), and coupled with capillary electrophoresis (CE) for the simultaneous selective extraction, separation and determination of trace phenolic compounds in water samples. The resultant mt-MIPs exhibited uniform spherical morphology, large specific surface area and high thermal stability, and offered high selectivity towards the six template phenolic compounds. Various parameters affecting the molecularly imprinted SPE (MISPE) efficiency were investigated in detail, and excellent CE separation was realized within 7min. Good linearity was obtained in the range of 1-200μgL-1 for phenol and 4-CP, and 1-300μgL-1 for 2,4,6-TCP, 2,4-DCP, 2-CP and 2,6-DCP. High sensitivity was attained with low limits of detection and quantification ranging from 0.17 to 0.31μgL-1 and 0.57 to 1.03μgL-1, respectively. Satisfactory recoveries for spiked reservoir water, river water, tannery wastewater and tap water samples were achieved in the range of 82.13-105.63% with relative standard deviations within 1.68-6.96%. The developed MISPE-CE method proved practically feasible for simultaneous selective extraction/enrichment, separation and sensitive determination of multiple targets in complicated aqueous matrices.