N. Jornet-Martínez

Sensitive and selective plasmonic assay for spermine as biomarker in human urine.

A simple, fast, and highly selective and sensitive colorimetric assay to detect nanomolar levels of spermine in human urine (healthy donors, cancer patients) is reported. This assay is based on the absence of a competitive organic capping on the gold nanoparticles together with the high affinity of the amine groups of the analyte for the nanoparticle surface.

On-line in-tube solid phase microextraction-capillary liquid chromatography method for monitoring degradation products of di-(2-ethylhexyl) phthalate in waters

The main di-(2-ethylhexyl) phthalate (DEHP) degradation products, (2-ethylhexyl) phthalate (MEHP), diethyl phthalate (DEP) and dibutyl phthalate (DBP), have been tested. The proposed cost-effective method combines on-line, in-tube solid-phase micro extraction (IT-SPME) in in-valve configuration and capillary liquid chromatography with UV diode array detection (Cap-LC-DAD). Acidification of the samples at pH 3 improved markedly the estimation of MEHP. Aliquots of 4mL of acidified water samples were directly processed. After sample loading, the analytes were desorbed with the mobile-phase and transferred to the monolithic capillary column. Satisfactory linearity and precision, absence of matrix effect and suitable limits of detection (LODs): 0.005, 0.1, 0.1 and 1.5μg/L for MEHP, DEP, DEHP and DBP, respectively have been achieved. The main advantages are speed and the reduction of background signal by minimizing sample preparation. Real water samples have been analyzed.

Estimation of the presence of unmetabolized dialkyl phthalates in untreated human urine by an on-line miniaturized reliable method.

At present, human exposure to dialkyl phthalates is assessed through urinary measurement of their metabolites due mainly to contamination in their analysis by their ubiquitous presence. An on-line miniaturized method and the processing of the untreated urine samples have been the key factors for minimizing contamination and achieving unbiased results. Di(2-ethylhexyl) (DEHP), diethyl (DEP), dibutyl (DBP) and mono-ethylhexyl (MEHP) phthalates in urine samples have been included in the study; MEHP as metabolite of the main dialkyl phthalate such as DEHP. On-line in-tube solid-phase microextraction (IT-SPME)-capillary liquid chromatography (CapLC) with diode array detection (DAD) is employed. The detection limits (LODs) achieved in urine were between 0.5 and 1.5 μg/L. Eighteen urines were processed. DBP and DEHP were found in nine and five samples, respectively and DEP in three of them. MEHP was only detected in one of the eighteen samples analyzed.

Zein as biodegradable material for effective delivery of alkaline phosphatase and substrates in biokits and biosensors.

A biodegradable material, zein, is proposed as a reagent delivery platform for biokits and biosensors based on alkaline phosphatase (ALP) activity/inhibition in the presence of phosphatase substrates. The immobilization and release of both the substrate and/or the active ALP, in a biodegradable and low-cost material such as zein, a prolamin from maize, and in combination with glycerol as plasticizer have been investigated. Three zein-based devices are proposed for several applications: (1) inorganic phosphorus estimation in water of different sources (river, lake, coastal water and tap water) with a detection limit of 0.2mg/L - compared to at least 1mg/L required by legislation, (2) estimation of ALP in saliva and (3) chlorpyrifos control in commercial preparations. The single-use kits developed are low cost, easy and fast to manufacture and are stable for at least 20 days at -20°C, so the zein film can preserve and deliver both the enzyme and substrates.

In tube-solid phase microextraction-nano liquid chromatography: Application to the determination of intact and degraded polar triazines in waters and recovered struvite

In-tube solid-phase microextraction (IT-SPME) coupled to miniaturized liquid chromatography (LC) techniques are attractive mainly due to the column efficiency improvement, sensitivity enhancement and reduction of solvent consumption. In addition, the nanomaterials based sorbents can play a key role in the improvement of the extraction efficiency taking into account their interesting physical and chemical properties. Thus, in this work the performance of IT-SPME coupled to nano LC (NanoLC) has been compared with the performance of IT-SPME coupled to capillary LC (CapLC) with similar configurations for the determination of polar triazines including their degradation products. In both cases, a DAD detector was used. Different extractive phases such as TRB-5, TRB-5/c-SWNTs, TRB-5/c-MWNTs capillary columns have been tested. The dimensions of the capillary columns were 0.32mm id×40cm length and 0.1 or 0.075mm i.d.×15cm length for the couplings with CapLC and NanoLC, respectively. The processed volume was 4mL for CapLC and 0.5mL for NanoLC. The elution was carried out with ACN:H2O (30:70, v/v). IT-SPME-NanoLC has shown a higher performance than IT-SPME-CapLC for the target analytes demonstrating the enhancement of the extraction efficiency with the former configuration. A new phase TEOS-MTEOS-SiO2NPs has been also proposed for IT-SPME-NanoLC, which improves the retention of polar compounds. Compared with previously published works, improved LODs were achieved (0.025-0.5μgL-1). The practical application of the proposed procedure has been demonstrated for the analysis of water samples and recovered struvite samples from wastewater treatment plants. Therefore, the proposed procedure can be an alternative method for regulatory purposes.

Development of a polydimethylsiloxane–thymol/nitroprusside composite based sensor involving thymol derivatization for ammonium monitoring in water samples

This report describes a polydimethylsiloxane (PDMS)-thymol/nitroprusside delivery composite sensor for direct monitoring of ammonium in environmental water samples. The sensor is based on a PDMS support that contains the Berthelots reaction reagents. To prepare the PDMS-thymol/nitroprusside composite discs, thymol and nitroprusside have been encapsulated in the PDMS matrix, forming a reagent release support which significantly simplifies the analytical measurements, since it avoids the need to prepare derivatizing reagents and sample handling is reduced to the sampling step. When, the PDMS-thymol/nitroprusside composite was introduced in water samples spontaneous release of the chromophore and catalyst was produced, and the derivatization reaction took place to form the indothymol blue. Thus, qualitative analysis of NH4(+) could be carried out by visual inspection, but also, it can be quantified by measuring the absorbance at 690 nm. These portable devices provided good sensitivity (LOD<0.4 mg L(-1)) and reproducibility (RSD <10%) for the rapid detection of ammonium. The PDMS-NH4(+) sensor has been successfully applied to determine ammonium in water samples and in the aqueous extracts of particulate matter PM10 samples. Moreover, the reliability of the method for qualitative analysis has been demonstrated. Finally, the advantages of the PDMS-NH4(+) sensor have been examined by comparing some analytical and complementary characteristics with the properties of well-established ammonium determination methods.

Microextraction with phases containing nanoparticles.

In this article, the state of the art of microextraction techniques that involve nanoparticles or nanomaterials (NPs) is reviewed, with special emphasis on the applications described in the biomedical field. The uses and advantages of the different types of NPs such as carbon nanotubes (either single- and multi-walled) and other carbon-based materials, metallic NPs, including gold, silver and magnetic NPs, and silica NPs are summarized. The main strategies used to modify the selectivity, extractive capacity and/or the stability of NPs through a chemical reaction are also reviewed. The potential advantages of NPs in different forms of off-line and on-line microextraction are discussed, and illustrative examples of application in the biomedical field are shown.

Analysis of Contact Traces of Cannabis by In-Tube Solid-Phase Microextraction Coupled to Nanoliquid Chromatography

Because of its inherent qualities, in-tube solid-phase microextraction (IT-SPME) coupled on-line to nanoliquid chromatography (nanoLC) can be a very powerful tool to address the new challenges of analytical laboratories such as the analysis of traces of complex samples. This is the case of the detection of contact traces of drugs, especially cannabis. The main difficulties encountered in the analysis of traces of cannabis plants on surfaces are the low amount of sample available (typically < 1 mg), the complexity of the matrix, and the low percentages of cannabinoic compounds in the samples. In this work, a procedure is described for the detection of residues of cannabis on different surfaces based on the responses obtained by IT-SPME coupled to nanoLC with UV diode array detection (DAD) for the cannabinoids Δ9-tetrahydrocannabinol (THC), cannabidiol (CBD), and cannabinol (CBN); the proposed conditions can also be applied for quantitative purposes through the measurement of the percentage of THC, the most abundant cannabinoid in plants. The method is based on collecting the suspected drug samples with cotton swabs, followed by the extraction of the target compounds by ultrasound assisted extraction. The extracts are then separated and processed by IT-SPME-nanoLC. The proposed approach has been applied to the detection of traces of cannabis in different kind of items (plastic bags, office paper, aluminum foil, cotton cloths, and hand skin). Sample amounts as low as 0.08 mg have been collected and analysed for THC. The selectivity and effect of the storage conditions on the levels of THC have also been evaluated. The percentages of THC in the samples typically ranged from 0.6% to 2.8%, which means that amounts of this compound as low as 1–2 µg were adequately detected and quantified. For the first time, the reliability of IT-SPME-nanoLC for the analysis of complex matrices such as cannabis plant extracts has been demonstrated.

Delivering Inorganic and Organic Reagents and Enzymes from Zein and Developing Optical Sensors

Nowadays, interest in using environmentally friendly materials is increasing in many fields. However, the rational design of sensors with biodegradable materials is a challenge. The main aim of this work is to show the possibility of using zein, a protein from corn, as a biodegradable and low-cost material for immobilizing, stabilizing, and delivering different kind of reagents for developing optical sensors. Enzymes, metallic salts, and aromatic and small organic compounds were tested. In addition, different techniques of immobilization, entrapment and adsorption, were used, and different formats, such as solid devices and also multiwell platforms, were proposed. The capacity of zein for immobilizing two reagents together, enzyme and substrate, into a multianalysis format was also shown. Two applications were developed as examples: a colorimetric assay based on a ferric hydroxamate reaction for ester drugs, which was applied in atropine determination in pills, and a fluorimetric enzymatic multiwell-plate biodevice applied in phosphate determination in human serum and urine. Zein demonstrated being not only a green alternative but also a versatile polymer for developing sensors from reagents with different natures in different formats and matrices, thereby resulting in different applications.