Magnetic molecularly imprinted polymer for the simultaneous selective extraction of phenoxy acid herbicides from environmental water samples.

A selective magnetic molecularly imprinted polymer (MMIP) was synthetized with 4-chloro-2-methylphenoxyacetic acid as template and 4-vinylpiridine as monomer in presence of vinylized magnetite nanoparticles. Scanning electron microscopy, nitrogen adsorption-desorption isotherms, Fourier transform infrared spectrometry and vibrating sample magnetometry were applied to characterize the resulting material. The synthesized MMIP was applied as sorbent in magnetic molecularly imprinted solid-phase extraction (MMISPE) for selective extraction of a mixture of the five herbicides 4-chloro-2-methylphenoxyacetic acid (MCPA), 4-(4-chloro-2-methylphenoxy)butyric acid (MCPB), mecoprop (MCPP), fenoxaprop (FEN) and haloxyfop (HAL). Several parameters affecting the extraction conditions were optimized to achieve the best extraction performance. The best MMISPE combined with HPLC-DAD gave detection and quantification limits between 0.33 and 0.71 µg L-1 and 1.1-2.4 µg L-1, respectively, were obtained. The precision of the whole method provided RSD values below 7.3%, and the accuracy was demonstrated by the analysis of several water samples of different origins, with recoveries ranged from 77 to 98%. Moreover, a remarkable re-usability of the MMIP sorbent, more than 65 uses without losses in extraction capacity, was obtained.

Preparation of monolithic polymer-magnetite nanoparticle composites into poly(ethylene-co-tetrafluoroethylene) tubes for uses in micro-bore HPLC separation and extraction of phosphorylated compounds.

This paper describes the fabrication of a novel microbore monolithic column modified with magnetite nanoparticles (MNPs) prepared in a poly(ethylene-co-tetrafluoroethylene) (EFTE) tubing, and its application as stationary phase for the chromatographic separation of phosphorylated compounds. In order to obtain the composite column, a two-step procedure was performed. The formation of a glycidyl methacrylate-based monolith inside the activated ETFE tube was firstly carried out. Then, two incorporation approaches of MNPs in monoliths were investigated. The generic polymer was modified with 3-aminopropyltrimethoxysilane (APTMS) to be subsequently attached to MNP surfaces. Alternatively, APTMS-coated MNPs were firstly prepared and subsequently used for attachment onto the monolith surface through reaction of epoxy groups present in the generic monolith. This last strategy gave a reproducible layer of MNPs coated onto the polymer monolith as well as robust and permeable chromatographic columns. The retention behaviour of this MNP-based composite monolithic column was studied by using small phosphorylated compounds (adenosine phosphates). It was found that the retention of model analytes was ruled by partitioning and adsorption HILIC mechanisms. The columns also exhibited satisfactory performance in the separation of these target compounds, showing good chromatographic behaviour after two months of continued use. These composite monolithic columns were also successfully applied to the extraction of a tryptic digest of ß-casein.

Extraction and preconcentration of organophosphorus pesticides in water by using a polymethacrylate-based sorbent modified with magnetic nanoparticles.

A polymethacrylate-based sorbent modified with magnetic nanoparticles (MNPs) has been synthesized and used as sorbent for solid-phase extraction (SPE) and magnetic solid-phase extraction (MSPE) of three organophosphorus pesticides (phosmet, pirimiphos-methyl, and chlorpyrifos) in water samples followed by high-performance liquid chromatography-diode array detection. The sorbent was prepared from a glycidyl methacrylate-based polymer, modified with a silanizing agent, followed by immobilization of MNPs on the surface of the material. The sorbent was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. Comparative studies of this support were done both in conventional SPE cartridge and MSPE approach. Several extraction parameters (loading pH, elution solvent, eluting volume, and loading flow rate) were investigated in detail. Under optimal conditions, the proposed sorbent gave an excellent enrichment efficiency of analytes and detection limits between 0.01 and 0.25 µg L-1. The recoveries of organophosphorus pesticides in spiked water samples were in the range of 71-98%, and the developed sorbent showed a high reusability (up to 50 uses without losses in recovery). The proposed method was satisfactorily applied to the analysis of these pesticides in water samples from different sources.

Selective and Sensitive Chemiluminescence Determination of MCPB: Flow Injection and Liquid Chromatography.

Two new chemiluminescence (CL) methods are described for the determination of the herbicide 4-(4-chloro-o-tolyloxy) butyric acid (MCPB). First, a flow injection chemiluminescence (FI-CL) method is proposed. In this method, MCPB is photodegraded with an ultraviolet (UV) lamp and the photoproducts formed provide a great CL signal when they react with ferricyanide in basic medium. Second, a high-performance liquid chromatography chemiluminescence (HPLC-CL) method is proposed. In this method, before the photodegradation and CL reaction, the MCPB and other phenoxyacid herbicides are separated in a C18 column. The experimental conditions for the FI-CL and HPLC-CL methods are optimized. Both methods present good sensitivity, the detection limits being 0.12 µg L(-1) and 0.1 µg L(-1) (for FI-CL and HPLC-CL, respectively) when solid phase extraction (SPE) is applied. Intra- and interday relative standard deviations are below 9.9%. The methods have been satisfactorily applied to the analysis of natural water samples. FI-CL method can be employed for the determination of MCPB in simple water samples and for the screening of complex water samples in a fast, economic, and simple way. The HPLC-CL method is more selective, and allows samples that have not been resolved with the FI-CL method to be solved.

Determination of organothiophosphorus pesticides in water by liquid chromatography and post-column chemiluminescence with cerium(IV).

A new, fast, selective and sensitive method has been developed for the simultaneous determination of nine organothiophosphorus (OTP) pesticides, namely omethoate, dimethoate, disulfoton-sulfoxide, methidathion, phosmet, malathion, diazinon, pirimiphos-methyl and chlorpyrifos. The pesticides were separated on a Kinetex C18 column by gradient elution with acetonitrile:water. A post-column basic hydrolysis of the pesticides and later a chemiluminescence (CL) reaction with cerium (IV) in acid medium was carried out. Hexadecylpyridinium chloride highly enhanced the CL emission. Under optimized conditions, linearity, precision, limits of detection and quantification, and accuracy were determined. Both selectivity and sensitivity were compared with those obtained with UV detection. In combination with SPE, limits of detection in the range 15-80ng/L and 5-30ng/L were obtained when 250mL and 1000mL of solution were treated, respectively. When applied to 250mL of sample the inter-day precision of the method was between 3.5% and 7.3% and the intra-day precision between 2.9% and 6.0%. The method was applied to determine OTP pesticides in spiked water samples from different origins: irrigation, river, sea, ground, spring, mineral and tap waters, being the percentage of recovery of added amounts near 100% form most of the pesticides.