Publications by authors named "Francisco Pena-Pereira"

Molecular imprinting technology is well established in areas where a high selectivity is required, such as catalysis, sensing, and separations/sample preparation. However, according to the Principles of Green Chemistry, it is evident that the various steps required to obtain molecularly imprinted polymers (MIPs) are far from ideal. In this regard, greener alternatives to the synthesis of MIPs have been proposed in recent years.

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In this work, two sensitive droplet-based luminescent assays with smartphone readout for the determination of trimethylamine nitrogen (TMA-N) and total volatile basic nitrogen (TVB-N) are reported. Both assays exploit the luminescence quenching of copper nanoclusters (CuNCs) produced when exposed to volatile nitrogen bases. In addition, hydrophobic-based cellulose substrates demonstrated their suitability as holders for both in-drop volatile enrichment and subsequent smartphone-based digitization of the enriched colloidal solution of CuNCs.

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The growing interest in the development of cost-effective, straightforward, and rapid analytical systems has found cellulose-based materials, including cellulose derivatives, cellulose-based gels, nanocellulosic materials, and the corresponding (nano)cellulose-based composites, to be valuable platforms for sensor development. The present work presents recent advances in the development of cellulose-based sensors for the determination of volatile analytes and derivatives of analytical relevance. In particular, strategies described in the literature for the fabrication and modification of cellulose-based substrates with responsive materials are summarized.

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The present work reports on the assessment of widely available waterproof cellulose-based substrates for the development of sensitive in-drop plasmonic sensing approaches. The applicability of three inexpensive substrates, namely, Whatman 1PS, polyethylene-coated filter paper, and tracing paper, as holders for microvolumes of colloidal solutions was evaluated. Waterproof cellulose-based substrates demonstrated to be highly convenient platforms for analytical purposes, as they enabled generation of volatiles and syringeless drop exposure unlike conventional single-drop microextraction approaches and can behave as sample compartments for smartphone-based colorimetric sensing in an integrated way.

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Lab-on-paper technologies, also known as paper-based analytical devices (PADs), have received increasing attention in the last years, and nowadays, their use has spread to virtually every application area, i.e., medical diagnostic, food safety, environmental monitoring, etc.

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The present work reports on the assessment of luminescent probes derived from citric acid (CA) and β-aminothiols (namely, l-cysteine (Cys) and cysteamine) for instrumental and smartphone-based fluorimetric sensing purposes. Remarkably, the evaluated luminescent probes derived from natural compounds showed pH-dependent dual excitation/dual emission features. Both fluorophores hold promise for the ratiometric fluorimetric sensing of pH, being especially convenient for the smartphone-based sensing of pH via ratiometric analysis by proper selection of B and G color channels.

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The determination of contaminants of emerging concern (CECs) in environmental samples has become a challenging and critical issue. The present work focuses on miniaturized analytical strategies reported in the literature for the determination of CECs. The first part of the review provides brief overview of CECs whose monitoring in environmental samples is of particular significance, namely personal care products, pharmaceuticals, endocrine disruptors, UV-filters, newly registered pesticides, illicit drugs, disinfection by-products, surfactants, high technology rare earth elements, and engineered nanomaterials.

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The development of disposable sensors that can be easily adapted to every analytical problem is currently a hot topic that is revolutionizing many areas of science and technology. The need for decentralized analytical measurements at real time is increasing for solving problems in areas such as environment pollution, medical diagnostic, food quality assurance, etc., requiring fast action.

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Green analytical chemistry focuses on making analytical procedures more environmentally benign and safer to humans. The amounts and toxicity of reagents, generated waste, energy requirements, the number of procedural steps, miniaturization, and automation are just a few of the multitude of criteria considered when assessing an analytical methodology's greenness. The use of greenness assessment criteria requires dedicated tools.

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Ionic liquids (ILs) are used in various fields of chemistry. One of them is CO capture, a process that is quite well described. The solubility of CO in ILs can be used as a model to investigate gas absorption processes.

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The use of paper-based devices in combination with noninstrumental detection systems is becoming increasingly important in the analytical field due to its simplicity, rapidity, and low cost. However, their use for determination of volatile analyte derivatives is still relatively scarce. The present work reports on the assessment of a paper-based gas-sensing approach for the simultaneous noninstrumental colorimetric detection of nitrite and sulfide.

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The present work reports on the combination of paper-based analytical devices (PADs) and information technology (IT) equipment for non-instrumental determination of boron. PADs prepared with curcumin as a receptor and ethanolic extracts of Curcuma longa L. powder were evaluated for sensing.

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Due to various desirable physicochemical properties, ionic liquids (ILs) are still gaining in popularity. ILs have been recurrently considered green solvents. However, environmental, health and safety assessments of ILs have raised certain doubts about their benignness, and their greenness status is currently unclear.

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A novel method for AuNPs/total Au speciation based on the combination of magnetic solid phase extraction and graphite furnace atomic absorption spectrometry (GFAAS) is described. Ascorbic acid enabled the quantitative extraction of both AuNPs and Au(III) by naked FeONPs, whereas a selective extraction of AuNPs was achieved in the presence of sodium thiosulfate. Experimental parameters influencing the extraction of both AuNPs and total Au, namely FeONPs mass, L-ascorbic acid concentration, pH, extraction time, sample volume, NaSO concentration and re-dispersion volume of magnetic solid phase prior to introduction in the graphite tube, were evaluated.

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Organic solvents are ubiquitous in chemical laboratories and the Green Chemistry trend forces their detailed assessments in terms of greenness. Unfortunately, some of them are not fully characterized, especially in terms of toxicological endpoints that are time consuming and expensive to be determined. Missing values in the datasets are serious obstacles, as they prevent the full greenness characterization of chemicals.

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This work reports on the implementation of gold nanorods (AuNRs) in headspace solvent microextraction for colorimetric determination of volatile analyte derivatives in a single drop. The exposure of AuNRs to both HSe and elemental mercury (Hg) results in a shift of the longitudinal plasmonic band, unlike a number of volatiles. Accordingly, a method is reported for the determination of Hg with potential applicability to the determination of thiomersal (sodium ethylmercurithiosalicylate).

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A rapid, simple and affordable method for arsenic speciation analysis is described in this work. The proposed methodology involves in situ arsine generation, transfer of the volatile to the headspace and its reaction with silver nitrate at the detection zone of a paper-based analytical device (PAD). Thus, silver nitrate acts as a recognition element for arsine in the paper-based sensor.

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The study presents the result of the application of chemometric tools for selection of physicochemical parameters of solvents for predicting missing variables - bioconcentration factors, water-octanol and octanol-air partitioning constants. EPI Suite software was successfully applied to predict missing values for solvents commonly considered as "green". Values for logBCF, logK and logK were modelled for 43 rather nonpolar solvents and 69 polar ones.

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This work reports on the development of a novel methodology for bromide determination by combining headspace single-drop microextraction with microvolume fluorospectrometry. The method lies in the in situ generation of bromine, transfer of the volatile to the headspace and trapping/reaction onto a fluorescein-containing aqueous drop exposed to the gas phase. The decrease in the fluorescence intensity enabled the determination of bromide without dilution of the enriched microdrop.

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An overview of the combination of liquid-phase microextraction (LPME) techniques with graphite furnace atomic absorption spectrometry (GFAAS) is reported herein. The high sensitivity of GFAAS is significantly enhanced by its association with a variety of miniaturized solvent extraction approaches. LPME-GFAAS thus represents a powerful combination for determination of metals, metalloids and organometallic compounds at (ultra)trace level.

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This work describes a fast and simple assay for in situ detection of thiocyanate, i.e., a biomarker of tobacco smoke exposure, in human saliva.

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In this work, hybrid silica-based materials with immobilized ionic liquids (ILs) were prepared by sol-gel technology and evaluated as solid-phase microextraction (SPME) fiber coatings. High loadings of the IL 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide ([C4MIM][TFSI]) were confined within the hybrid network. Coatings composition and morphology were evaluated using scanning electron microscopy and energy dispersive X-ray spectrometry.

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In recent years, ionic liquids and deep eutectic mixtures have demonstrated great potential in extraction processes relevant to several scientific and technological activities. This review focuses on the applicability of these sustainable solvents in a variety of extraction techniques, including but not limited to liquid- and solid-phase (micro) extraction, microwave-assisted extraction, ultrasound-assisted extraction and pressurized liquid extraction. Selected applications of ionic liquids and deep eutectic mixtures on analytical method development, removal of environmental pollutants, selective isolation, and recovery of target compounds, purification of fuels, and azeotrope breaking are described and discussed.

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The development of a novel methodology for extraction and preconcentration of the most commonly used anionic surface active agents (SAAs), linear alkylbenzene sulfonates (LAS), is presented herein. The present method, based on the use of silica-magnetite nanoparticles modified with cationic surfactant aggregates, was developed for determination of C10-C13 LAS homologues. The proposed methodology allowed quantitative recoveries of C10-C13 LAS homologues by using a reduced amount of magnetic nanoparticles.

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