Fernando Maya

Automatic determination of copper by in-syringe dispersive liquid–liquid microextraction of its bathocuproine-complex using long path-length spectrophotometric detection

The recently proposed concept of automatic in-syringe dispersive liquid-liquid microextraction was successfully applied to the determination of copper in environmental water samples. Bathocuproine was added to the organic phase as a selective reagent, resulting in the formation of a complex with copper. Dispersion was achieved by aspiration of the organic phase and then the watery phase into the syringe as rapidly as possible. After aggregation of the solvent droplets at the head of the syringe, the organic phase was pushed into a liquid waveguide capillary cell for highly sensitive spectrophotometric detection. The entire analytical procedure was carried out automatically on a multisyringe flow-injection analysis platform and a copper determination was accomplished in less than 220 s. A limit of detection of 5 nmol L(-1) was achieved at an extraction efficiency >90% and a preconcentration factor of 30. A linear working range for concentrations of up to 500 nmol L(-1) and an average standard deviation of 7% in peak height were found. The method proved to be well-suited for the determination of copper in water samples, with an average analyte recovery of 100.6%.

Interfacing on-line solid phase extraction with monolithic column multisyringe chromatography and chemiluminescence detection: An effective tool for fast, sensitive and selective determination of thiazide diuretics.

A new, multisyringe flow injection set-up has been developed for the completely automated determination of trace thiazide compounds with diuretic action in different types of samples. The proposed instrumental set-up exploits for the first time, a low pressure on-line solid phase extraction-liquid chromatography-chemiluminescence detection method. This novel combination of sample treatments in flow systems expands the current applicability of low pressure liquid chromatography due to the isolation/preconcentration of the target compounds, besides high selectivity and sensitivity. For the determination of three thiazide compounds named hydroflumethiazide, furosemide and bendroflumethiazide, the proposed set-up provided with the preconcentration of only 1mL of sample, limits of detection of 3, 60 and 40microgL(-1), respectively. Furthermore wide linear dynamic ranges of 6-4000, 140-20,000 and 90-40,000microgL(-1), respectively, were obtained. Besides of this, a high injection throughput of 12h(-1) was also achieved. As in sports, thiazide diuretics are prohibited substances, the proposed method has been applied to their determination in urine samples. Furthermore the potential of the proposed method as a fast-screening approach for emerging contaminants in waters has been also tested by applying it to well water and leachates from a solid waste landfill.

Automatic In-Syringe Dispersive Microsolid Phase Extraction Using Magnetic Metal–Organic Frameworks

A novel automatic strategy for the use of micro- and nanomaterials as sorbents for dispersive microsolid phase extraction (D-μ-SPE) based on the lab-in-syringe concept is reported. Using the developed technique, the implementation of magnetic metal-organic framework (MOF) materials for automatic solid-phase extraction has been achieved for the first time. A hybrid material based on submicrometric MOF crystals containing Fe3O4 nanoparticles was prepared and retained in the surface of a miniature magnetic bar. The magnetic bar was placed inside the syringe of an automatic bidirectional syringe pump, enabling dispersion and subsequent magnetic retrieval of the MOF hybrid material by automatic activation/deactivation of magnetic stirring. Using malachite green (MG) as a model adsorption analyte, a limit of detection of 0.012 mg/L and a linear working range of 0.04-2 mg/L were obtained for a sample volume equal to the syringe volume (5 mL). MG preconcentration was linear up to a volume of 40 mL, obtaining an enrichment factor of 120. The analysis throughput is 18 h(-1), and up to 3000 extractions/g of material can be performed. Recoveries ranging between 95 and 107% were obtained for the analysis of MG in different types of water and trout fish samples. The developed automatic D-μ-SPE technique is a safe alternative for the use of small-sized materials for sample preparation and is readily implementable to other magnetic materials independent of their size and shape and can be easily hyphenated to the majority of detectors and separation techniques.

Porous polymer monoliths with large surface area and functional groups prepared via copolymerization of protected functional monomers and hypercrosslinking

A new approach to the preparation of porous polymer monoliths possessing both large surface area and functional groups has been developed. The chloromethyl groups of poly(styrene-co-4-acetoxystyrene-co-vinylbenzyl chloride-co-divinylbenzene) monolith enable post-polymerization hypercrosslinking catalyzed by ferric chloride in dichloroethane leading to a multitude of small pores thus enhancing the surface area. The acetoxy functionalities are easily deprotected using hydrazine to produce polar phenolic hydroxyl groups, which would be difficult to obtain by direct copolymerization of hydroxyl-containing monomers. The hypercrosslinking and deprotection reactions as well as their sequence were studied in detail with bulk polymer monoliths containing up to 50% 4-acetoxystyrene and its progress monitored by infrared spectrometry and nitrogen adsorption/desorption measurements. No significant difference was found for both possible successions. All monoliths were also prepared in a capillary column format, then deprotected and hypercrosslinked. Capillary columns were tested for the separation of small molecules using reversed phase and normal phase chromatographic modes. For polymer monoliths containing 50% deprotected 4-acetoxystyrene, column efficiencies of 40,000 plates/m for benzene in reversed phase mode and 31,800 plates/m for nitrobenzene in normal phase mode, were obtained. The percentage of hydroxyl groups in the monoliths enables modulation of polarity of the stationary phase. They also represent functionalities that are potentially suitable for further modifications and formation of new types of stationary phases for liquid chromatography.

Fully-automated in-syringe dispersive liquid-liquid microextraction for the determination of caffeine in coffee beverages.

A novel fully-automated magnetic stirring-assisted lab-in-syringe analytical procedure has been developed for the fast and efficient dispersive liquid-liquid microextraction (DLLME) of caffeine in coffee beverages. The procedure is based on the microextraction of caffeine with a minute amount of dichloromethane, isolating caffeine from the sample matrix with no further sample pretreatment. Selection of the relevant extraction parameters such as the dispersive solvent, proportion of aqueous/organic phase, pH and flow rates have been carefully evaluated. Caffeine quantification was linear from 2 to 75mgL(-1), with detection and quantification limits of 0.46mgL(-1) and 1.54mgL(-1), respectively. A coefficient of variation (n=8; 5mgL(-1)) of a 2.1% and a sampling rate of 16h(-1), were obtained. The procedure was satisfactorily applied to the determination of caffeine in brewed, instant and decaf coffee samples, being the results for the sample analysis validated using high-performance liquid chromatography.

Improved spectrophotometric determination of paraquat in drinking waters exploiting a Multisyringe liquid core waveguide system.

A novel Multisyringe flow injection analysis (MSFIA) system combined with a 200 cm long pathlength liquid core waveguide (LCW) has been developed enabling for the first time the sensitive spectrophotometric determination at μg L(-1) levels of the herbicide paraquat (Pq(2+)) in drinking waters. The proposed system is a simple, economic and fast alternative for obtaining the first evidence of paraquat pollution prior the use of more complex instrumental techniques. The proposed methodology is based on the production of a blue free radical by reaction of Pq(2+) with ascorbic acid (partially oxidized with potassium iodate) in basic medium. Limits of detection and quantification as low as 0.7 and 2.3 μg L(-1), were obtained respectively. The working range is linear up to a concentration of 250 μg L(-1) of Pq(2+). The injection throughput of the proposed method is 34 h(-1). The results obtained with the LCW are compared with those using a conventional 1cm flow cell. The automation of standard addition procedures has been studied and implemented for samples causing matrix effects. Finally the proposed system has been applied to the determination of paraquat in drinking water samples.

Spectrophotometric determination of chloride in waters using a multisyringe flow injection system

A multisyringe flow injection system (MSFIA) with spectrophotometric detection is proposed as a fast, robust and low-reagent consumption system for the determination of chloride (Cl(-)) in waters. The system is based in the classic reaction of Cl(-) with Fe(3+) and Hg(SCN)(2), but due to the hazardous properties of this last reagent, the proposed methodology has been developed with the aim to minimize the consumption of this one, consuming less than 0.05 mg of Hg for a Cl(-) determination, being the system of this type with the lowest Hg consumption. The linear working range was between 1 and 40 mg L(-1) Cl(-) and the detection limit was 0.2 mg L(-1) Cl(-). The repeatability (RSD) was 0.8% for a 10 mg L(-1) Cl(-) solution, and the injection throughput was 130 h(-1). The proposed system is compared with other chloride monitoring flow systems, this comparison is realized with a point of view of the equilibrium between the obtained analytical features and produced residues toxicity. The proposed system was applied to the determination of Cl(-) in mineral, tap and well water.

Zeolitic imidazolate framework dispersions for the fast and highly efficient extraction of organic micropollutants

Development of advanced strategies for the extraction and preconcentration of trace levels of pollutants is essential for the quality control of water resources. A new procedure for the fast and highly efficient extraction of organic micropollutants from water using dispersions of zeolite imidazolate framework-8 (ZIF-8) crystals in a mixture of solvents is reported. The synergistic effect of using ZIF-8 dispersions in mixtures of water miscible and immiscible solvents enhances mass transfer and greatly improves extraction kinetics and capacity in comparison with the use of porous crystals or solvent microextraction separately. The effect of the ZIF-8 crystal size and surface composition has been evaluated using four different ZIF-8 samples spanning the micro- to nanometer range. The relevant parameters involved in the extraction such as the composition of the dispersion medium, the amount of ZIF-8 crystals, the extraction time, or the volume of dispersion required to ensure the maximum extraction efficiency, has also been studied using diethyl phthalate as a model compound. The use of 26 nm ZIF-8 crystals obtained using n-butylamine modulated synthesis has shown very fast extraction kinetics and excellent enrichment factors ranging from 150 to 380 for a mixture of six phthalate esters listed as priority pollutants by the United States EPA, allowing detection limits below the ng L−1 to be reached.

Flow analysis techniques as effective tools for the improved environmental analysis of organic compounds expressed as total indices.

The scope of this work is the accomplishment of an overview about the current state-of-the-art flow analysis techniques applied to the environmental determination of organic compounds expressed as total indices. Flow analysis techniques are proposed as effective tools for the quick obtention of preliminary chemical information about the occurrence of organic compounds on the environment prior to the use of more complex, time-consuming and expensive instrumental techniques. Recently improved flow-based methodologies for the determination of chemical oxygen demand, halogenated organic compounds and phenols are presented and discussed in detail. The aim of the present work is to demonstrate the highlight of flow-based techniques as vanguard tools on the determination of organic compounds in environmental water samples.

Submicrometric Magnetic Nanoporous Carbons Derived from Metal–Organic Frameworks Enabling Automated Electromagnet-Assisted Online Solid-Phase Extraction

We present the first application of submicrometric magnetic nanoporous carbons (μMNPCs) as sorbents for automated solid-phase extraction (SPE). Small zeolitic imidazolate framework-67 crystals are obtained at room temperature and directly carbonized under an inert atmosphere to obtain submicrometric nanoporous carbons containing magnetic cobalt nanoparticles. The μMNPCs have a high contact area, high stability, and their preparation is simple and cost-effective. The prepared μMNPCs are exploited as sorbents in a microcolumn format in a sequential injection analysis (SIA) system with online spectrophotometric detection, which includes a specially designed three-dimensional (3D)-printed holder containing an automatically actuated electromagnet. The combined action of permanent magnets and an automatically actuated electromagnet enabled the movement of the solid bed of particles inside the microcolumn, preventing their aggregation, increasing the versatility of the system, and increasing the preconcentration efficiency. The method was optimized using a full factorial design and Doehlert Matrix. The developed system was applied to the determination of anionic surfactants, exploiting the retention of the ion-pairs formed with Methylene Blue on the μMNPC. Using sodium dodecyl sulfate as a model analyte, quantification was linear from 50 to 1000 μg L(-1), and the detection limit was equal to 17.5 μg L(-1), the coefficient of variation (n = 8; 100 μg L(-1)) was 2.7%, and the analysis throughput was 13 h(-1). The developed approach was applied to the determination of anionic surfactants in water samples (natural water, groundwater, and wastewater), yielding recoveries of 93% to 110% (95% confidence level).