Synthesis of a novel magnetic nanomaterial for the development of a multielemental speciation method of lead, mercury, and vanadium via HPLC-ICP MS.

A new magnetic functionalized material based on graphene oxide magnetic nanoparticles named by us, M@GO-TS, was designed and characterized in order to develop a magnetic solid-phase extraction method (MSPE) to enrich inorganic and organic species of lead, mercury, and vanadium. A flow injection (FI) system was used to preconcentrate the metallic and organometallic species simultaneously, while the ultra-trace separation and determination of the selected species were achieved by high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP MS). Therefore, preconcentration and separation/determination processes were automated and conducted separately. To the best of our knowledge, this is the first method combining an online MSPE and HPLC-ICP MS for multielemental speciation. Under the optimized conditions, the enrichment factor obtained for PbII, trimethyllead (TML), HgII, methylmercury (MetHg), and VV was 27. The calculated LOD for all studied species were as follows: 5 ng L-1, 20 ng L-1, 2 ng L-1, 10 ng L-1, and 0.4 ng L-1, respectively. The RSD values calculated with a solution containing 0.5 µg L-1 of all species were between 2.5 and 4.5%. The developed method was validated by analyzing Certified Reference Materials TMDA 64.3 for total concentration and also by recovery analysis of the species in human urine from volunteers and a seawater sample collected in Málaga. The t statistical test showed no significant differences between the certified and found values for TMDA 64.3. All the recoveries obtained from spiked human urine and seawater samples were close to 100%. All samples were analyzed using external calibration. The developed method is sensitive and promising for routine monitoring of the selected species in environmental waters and biological samples.

A Molecularly Imprinted Polypyrrole/GO@Fe3O4 Nanocomposite Modified Impedimetric Sensor for the Routine Monitoring of Lysozyme.

Lysozyme (LYS) applications encompass anti-bacterial activity, analgesic, and anti-inflammatory effects. In this work, a porous framework that was based on the polymerization of pyrrole (PPy) in the presence of multi-functional graphene oxide/iron oxide composite (GO@Fe3O4) has been developed. Oxygen-containing and amine groups that were present in the nanocomposite were availed to assembly LYS as the molecularly imprinted polymer (MIP) template. The synthesized material (MIPPy/GO@Fe3O4) was electrodeposited on top of a gold microelectrode array. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) were used to confirm the adequate preparation of GO@Fe3O4, and the characterization of the resulting molecularly imprinted electrochemical sensor (MIECS) was carried out by electrochemical impedance spectrometry (EIS), FT-IR analysis, and scanning electron microscopy (SEM). The impedimetric responses were analyzed mathematically by fitting to a Q(Q(RW)) equivalent circuit and quantitative determination of LYS was obtained in a linear range from 1 pg/mL to 0.1 µg/mL, presenting good precision (RSD ≈ 10%, n = 5) and low limit of detection (LOD = 0.009 pg/mL). The fabrication of this device is relatively simple, scalable, rapid, and economical, and the sensor can be used up to nine times without disintegration. The MIECS was successfully applied to the determination of LYS in fresh chicken egg white sample and in a commercial drug, resulting in a straightforward platform for the routine monitoring of LYS.

Comparative Study of Synthesis Methods to Prepare New Functionalized Adsorbent Materials Based on MNPs-GO Coupling.

In this work, the synthesis of new adsorbent nanomaterials based on the coupling of magnetic nanoparticles and graphene oxide (MNPs-GO) was addressed. Separately, MNPs and GO have adsorbent properties of great interest, but their use involves certain difficulties. The coupling seeks compensation for their disadvantages, while maintaining their excellent properties. Three different routes to synthesize coupled MNPs-GO were studied and are compared in this work. The three synthesized materials were functionalized with chelating groups: [1,5-bis (di-2-pyridyl) methylene] thiocarbonohydrazide (DPTH) and [1,5-bis(2-pyridyl)3-sulfophenylmethylene] thiocarbonohydrazide (PSTH). The new adsorbent nanomaterials were characterized adequately. Moreover, their capacities of adsorption toward heavy and noble metals were determined, in order to apply them as extractants in magnetic solid-phase extraction to preconcentrate metals in environmental samples. The results showed that one of the routes provided nanomaterials with better adsorbent characteristics and higher yields of functionalization.

Development of an on-line solid phase extraction method based on new functionalized magnetic nanoparticles. Use in the determination of mercury in biological and sea-water samples.

A new chelating sorbent which employs magnetic nanoparticles (MNPs) functionalized with 1,5-bis(di-2-pyridil)methylene thiocarbohydrazide (DPTH-MNPs) was synthetized and characterized. The aim of the synthesis of this material was to develop fast and simple methods for analysis of trace amounts of metal ions present in biological and environmental samples combining on-line magnetic solid phase microextraction (MSPME) with atomic spectrometry. The MNPs' magnetic core allows overcoming the backpressure problems that usually happen in SPME methods with NPs thanks to the possibility of immobilizing the MNPs by applying an external magnetic field. Thus, a flow injection FI-MSPME/cold vapor generation system coupled to an electrothermal atomic absorption spectrometer (CV-ETAAS) method for the determination of trace amounts of Hg in biological and sea-water samples was developed. A magnet based reactor designed to contain DPTH-MNPs was placed in the injection valve of the FI manifold. Several chemical and flow variables were considered as factors in the optimization process using central composite designs. With the optimized procedure, the detection limit obtained was 7.8ngL(-1) with a precision of 1.7% (RSD) (1.0µgL(-1) Hg). The linear range of the method was studied, and two sections of linear calibration were obtained: from determination limit (0.099µgL(-1)) to 10µgL(-1), and from 10µgL(-1) to at least 50µgL(-1). A preconcentration factor of 5.4 was calculated. The accuracy of the proposed method was demonstrated by analyzing three certified reference materials and by determining the analyte content in spiked sea-water samples. The determined values were in good agreement with the certified values and the recoveries for the spiked samples were in the range of 97.0-107.0%.

Multi-element determination of Pt, Pd and Ir traces in environmental samples by ICP-MS after pre-concentration.

An automated flow analysis method with on-line column pre-concentration/ inductively coupled plasma mass spectrometry (ICP-MS) was developed for the simultaneous determination of Pt, Pd and Ir in environmental samples. The system is based on retention of the analytes onto a column filled with 1,5-bis (2-pyridyl)-3-sulphophenyl methylene thiocarbonohydrazide immobilized on an aminopropyl-controlled pore glass (PSTH-cpg) placed in the injection valve of a simple flow manifold. The retained platinum group metals (PGMs) were subsequently eluted with a mixture of HNO(3) and thiourea. The effects of chemicals and flow variables were investigated. The optimized operating conditions were: sample pH 3.2, sample flow rate: 1.1 mL min(-1); eluent flow rate: 2.1 mL min(-1) and eluent 0.03% m/v thiourea solution in 3.2% (v/v) HNO(3). The detection limits obtained were 78.5 ng L(-1) for Pt, 55.5 ng L(-1) for Pd and 0.1 ng L(-1) for Ir. The enrichment factors were 18, 2.3 and 43 for Pt, Pd and Ir, respectively. The accuracy of the method was checked by the analysis of certified reference materials and by determining the analytes content in spiked environmental samples. Recovery was found to be in the range 93-107% in all cases.