New silica based adsorbent material from rice straw and its in-flow application to nitrate reduction in waters: Process sustainability and scale-up possibilities.

This paper shows a particular example to move to a sustainable circular economical process from valorization of rice straw ashes by developing a green synthesis for obtaining a useful sub-product. This strategy can palliate negative effects of the agriculture waste practices on the environment and also the obtained silica reduced nitrate content in waters. It is demonstrated that the silica synthesis developed at lab was scalable more than a hundred times with good results. Adsorption studies of nitrate in standards and real well waters at lab scale and scaling-up provided similar results. Adsorption values near to 15 mg/g for nitrate standards and 8.5 mg/g for well water were obtained until achieving the initial nitrate concentration. Experimental breakthrough curves fitted to Thomas model, which gave similar results for adsorption capacities. The adsorption capacity was checked with that obtained by a commercial resin, providing improved results. The method at large scale was compared with industrial traditional methods and green adsorbents.

Scopolamine analysis in beverages: Bicolorimetric device vs portable nano liquid chromatography.

Scopolamine (SCP) is often involved in sexual assaults and robberies, particularly in recreational environments. Therefore, analytical tools are required for the analysis of this compound amenable for the field. In this work, a sensor for SCP is described based on the entrapment of KMnO4 into polydimethylsiloxane (PDMS). The possibility of using KMnO4 in combination with the reagent 1,2-naphtoquinone-4-sulfonate (NQS) giving a double sensor acting as a bicolorimetric device is also demonstrated. In contact with the sample, the PDMS composite delivers MnO4-, which reacts rapidly with SCP under basic conditions causing a change of the color of the solution that can be related to the concentration of drug using both, absorbances and color coordinates, while the NQS part of the sensor remains unchanged. After an exposure time to the sensors of 10 min, satisfactory linearity was obtained for concentrations of SCP up to 865 µg/mL, being the limit of detection (LOD) 108 µg/mL. A method using a portable nano liquid chromatograph with detection at 255 nm has been also developed; in this case the LOD was 100 µg/mL and the working linear interval was 250-2000 µg/mL. The precision, expressed as relative standard deviation (RDS), was ≤8% for both methods. Different beverages (cola, cola-whisky, tonic water-vodka, red wine and green tea) were assayed. The potential of the two proposed approaches for on-site tests is discussed.

Modifying the reactivity of copper (II) by its encapsulation into polydimethylsiloxane: A selective sensor for ephedrine-like compounds.

This paper demonstrates that the reactivity of copper (II) can be modified through its entrappment in a polymeric matrix of polydimethylsiloxane (PDMS), which makes possible the reaction into the support instead of in solution. Amino-containing compounds such as amino acids, proteins and sugars, which react with Cu (II) in solution, do not react inside the polymer. As a prove of concept, a highly specific Cu (II) PDMS-based sensor for ephedrines has been developed in this work. When the sensors are put into contact with solutions of these drugs under basic conditions, a change in their color from pale green to purple is observed. This change enables the visual identification of ephedrine (Eph) in a few min, as well as its quantification using both reflectance diffuse measurements of the sensors and color intensities of their digitalized images. The sensors show suitable analytical performance for Eph-like compounds, and provide limits of detection (LODs) of 0.3-1.0 mg, and relative standard deviations (RDSs) < 10%. The method has been applied to both the qualitative and quantitative analysis of different types of liquid and solid samples (intravenous injection solution of Eph, dietary supplements and illicit drug-street samples) without the need of any special sample treatment.

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.

A solid colorimetric sensor for the analysis of amphetamine-like street samples.

A solid sensor obtained by embedding 1,2-naphthoquinone-4-sulfonate (NQS) into polydimethylsiloxane/tetraethylortosilicate/silicon dioxide nanoparticles composite has been developed to identify and determine amphetamine (AMP), methamphetamine (MAMP), 3,4-methylenedioxymetamphetamine (MDMA) and 3,4-methylenedioxyamphetamine (MDA). The analytes are derivatized inside the composite for 10 min to create a colored product which can be then quantified by measuring the diffuse reflectance or the color intensity after processing the digitalized image. Satisfactory limits of detection (0.002-0.005 g mL-1) and relative standard deviations (<10%) have been achieved. The proposed kit has been successfully validated and applied to the analysis of amphetamine-like drugs street samples. The kit allows the in-situ screening of the mentioned illicit drugs owing to its simplicity, rapidity and portability, with excellent sensor stability and at a very low-cost.

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.

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.

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 Berthelot's 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.

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.

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.