0000000000004747
AUTHOR
Juan L. Benedé
Carbon fibers as green and sustainable sorbent for the extraction of isoflavones from environmental waters.
Abstract Isoflavones are a group of phytoestrogens of important environmental concern due to their endocrine disrupting effects. This article presents a rapid, green, and sustainable method for determining four isoflavones (daidzein, genistein, formononetin, and biochanin A) in environmental waters complying with current trends in Analytical Chemistry. The method consists of in-syringe dispersive solid-phase extraction (DSPE) as the extraction approach, using carbon fibers as extraction material. The synthesis of carbon fibers is simple and sustainable, since it only requires a natural product such as raw cotton as precursor, which is thermally treated (600 °C for 30 min) in an inert (Ar) a…
Green determination of eight water-soluble B vitamins in cosmetic products by liquid chromatography with ultraviolet detection.
Abstract B vitamins are a group of compounds with beneficious properties for dermatologic care, and therefore they are included in the cosmetic formulations as high added-value ingredients. In this paper, an analytical method for the simultaneous determination of eight water-soluble B vitamins in cosmetic products is reported for the first time. This method is based on liquid chromatography with ultraviolet detection (LC-UV) analysis after simple water leaching of the analytes from the cosmetic matrix. No organic solvents are required, beyond the ethanol used in the chromatographic mobile phase. The proposed method has been successfully validated showing good linearity, limits of detection …
Determination of ultraviolet filters in bathing waters by stir bar sorptive–dispersive microextraction coupled to thermal desorption–gas chromatography–mass spectrometry
In this work, a new approach that combines the advantages of stir bar sorptive extraction (SBSE) and dispersive solid phase extraction (DSPE), i.e. stir bar sorptive-dispersive microextraction (SBSDµE), is employed as enrichment and clean-up technique for the sensitive determination of eight lipophilic UV filters in water samples. The extraction is accomplished using a neodymium stir bar magnetically coated with oleic acid-coated cobalt ferrite magnetic nanoparticles (MNPs) as sorbent material, which are detached and dispersed into the solution at high stirring rate. When stirring is stopped, MNPs are magnetically retrieved onto the stir bar, which is subjected to thermal desorption (TD) to…
Fundamentals and applications of stir bar sorptive dispersive microextraction: A tutorial review
Current trends in sample preparation focus on the miniaturization of the process resulting in what is known as microextraction techniques. Among them stir bar sorptive dispersive microextraction (SBSDME) is one of the most recent techniques. It was presented a few years ago as a hybrid microextraction technique that combines the principles of stir bar sorptive extraction (SBSE) and dispersive solid phase extraction (DSPE). This novel technique introduces, into the sample solution, a bar-shaped magnet coated with a magnetic (nano)material, which is maintained on the surface by magnetism. Once stirring starts, the competitive action between magnetism and rotational force is exploited. At low …
In-situ suspended aggregate microextraction: A sample preparation approach for the enrichment of organic compounds in aqueous solutions.
Abstract This work presents in-situ suspended aggregate microextraction (iSAME) as a new and expedient sample preparation method. This new concept capitalizes on the general principles of in-situ solvent formation microextraction, in the sense that extraction is carried out in a supramolecular aggregate phase, which is formed in-situ in the sample through one-step process involving ion-association between a cationic surfactant and a benzene sulfonic acid derivative. The suspended aggregate containing the analytes is then collected in the form of a thin-film on the surface of a common filter paper by suction filtration. The entrapped analytes are released by completely dissolving the thin-fi…
Determination of N-nitrosodiethanolamine in cosmetic products by reversed-phase dispersive liquid-liquid microextraction followed by liquid chromatography.
A new analytical method for the determination of N-nitrosodiethanolamine (NDELA), a very harmful compound not allowed in cosmetic products, is presented. The method is based on a new approach of dispersive liquid-liquid microextraction (DLLME) useful for extraction of highly polar compounds, called reversed-phase DLLME (RP-DLLME), followed by liquid chromatography-ultraviolet/visible (LC-UV/Vis) determination. The variables involved in the RP-DLLME process were studied to provide the best enrichment factors. Under the optimized conditions, a mixture of 750µL of acetone (disperser solvent) and 125µL of water (extraction solvent) was rapidly injected into 5mL of toluene sample solution. The e…
A rapid and sensitive gas chromatography-mass spectrometry method for the quality control of perfumes: simultaneous determination of phthalates
A rapid and sensitive analytical gas chromatography-mass spectrometry (GC-MS) method for perfume analysis to determine the phthalates banned by the European Union Regulation on cosmetic samples is presented. This method has been tested in commercial alcoholic perfume samples for the determination of the following seven phthalates: dibutyl phthalate, bis(2-ethylhexyl) phthalate, bis(2-methoxyethyl) phthalate, n-pentyl-isopentylphthalate, di-n-pentyl phthalate, diisopentylphthalate and benzyl butyl phthalate. Sample evaporation and redissolution in ethanol is carried out before GC-MS analysis, with no dilution of the sample. External calibration and standard addition calibration are compared …
Determination of UV filters in both soluble and particulate fractions of seawaters by dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry
An analytical method to determine the total content (i.e., not only in the soluble fraction but also in the particulate one) of eight commonly used UV filters in seawater samples is presented for the first time. Dispersive liquid-liquid microextraction (DLLME) is used as microextraction technique to pre-concentrate the target analytes before their determination by gas chromatography-mass spectrometry (GC-MS). In order to release the UV filters from the suspended particles an ultrasound treatment is performed before DLLME. The ultrasound treatment time was studied in order to achieve a quantitative lixiviation of the target analytes. The type and volume of both disperser and extraction solve…
Introducing a new and rapid microextraction approach based on magnetic ionic liquids: Stir bar dispersive liquid microextraction
With the aim of contributing to the development and improvement of microextraction techniques, a novel approach combining the principles and advantages of stir bar sorptive extraction (SBSE) and dispersive liquid-liquid microextraction (DLLME) is presented. This new approach, termed stir bar dispersive liquid microextraction (SBDLME), involves the addition of a magnetic ionic liquid (MIL) and a neodymium-core magnetic stir bar into the sample allowing the MIL coat the stir bar due to physical forces (i.e., magnetism). As long as the stirring rate is maintained at low speed, the MIL resists rotational (centrifugal) forces and remains on the stir bar surface in a manner closely resembling SBS…
Current trends on the determination of organic UV filters in environmental water samples based on microextraction techniques – A review
UV filters are a group of cosmetic ingredients commonly used in a wide variety of cosmetic products to protect users from UV solar radiation. They belong to different chemical families, such as benzophenones, p-aminobenzoates, salicylates, cinnamates, benzotriazoles, benzimidazoles, camphor derivatives, triazines, etc. These cosmetic ingredients are considered as emerging contaminants since they easily reach the aquatic environment, where they are accumulated causing harmful effects in the flora and fauna despite being present at the ng L-1 level. Therefore, the development of sensitive and selective analytical methods for their environmental surveillance monitoring is of high interest. In …
Stir bar sorptive-dispersive microextraction for trace determination of triphenyl and diphenyl phosphate in urine of nail polish users
Abstract This work describes a new analytical method useful for monitoring the human exposure to the endocrine-disrupting plasticizer triphenyl phosphate (TPP) via nail polish use. The method allows trace determination of this parent compound and its main metabolite, namely diphenyl phosphate (DPP), in urine samples of nail polish users. The method is based on a novel microextraction technique termed stir bar sorptive-dispersive microextraction (SBSDME) using a magnetic composite made of CoFe2O4 magnetic nanoparticles embedded into a mixed-mode weak anion exchange polymer (Strata™-X-AW), followed by liquid chromatography-tandem mass spectrometry (LC–MS/MS). The main parameters involved in t…
Stir bar sorptive-dispersive microextraction mediated by magnetic nanoparticles-nylon 6 composite for the extraction of hydrophilic organic compounds in aqueous media.
A new and sensitive analytical method based on the recently developed approach termed stir bar-sorptive dispersive microextraction (SBSDME) using a magnetic CoFe2O4@SiO2-nylon 6 composite as sorbent material is presented for the extraction of hydrophilic organic compounds. The simultaneous determination of four hydrophilic UV filters in environmental water samples has been chosen as a model analytical application due to the increasing awareness regarding the occurrence of sunscreen residuals in natural waters. The developed SBSDME approach combines the principles and benefits of stir bar sorptive extraction (SBSE) and dispersive solid phase extraction (DSPE) but allows for lower extraction …
Synergistic combination of polyamide-coated paper-based sorptive phase for the extraction of antibiotics in saliva.
Abstract The development of analytical methods that allow the simultaneous determination of a wide range of analytes with different properties is one of the focuses of attention in Analytical Chemistry. This work describes a proof-of-concept of the synergistic extraction of a planar paper-based sorptive phase modified with a polyamide such as nylon. This as-prepared sorptive phase enables the extraction of six penicillin-derived antibiotics of different polarity from human saliva samples in the same analysis, since the analytes either interact with the paper or with the nylon. The synthesis of the sorptive phase is simple as it only requires dipping the paper into an organic solution of the…
Environmental Monitoring of Cosmetic Ingredients
Abstract Since the late 1990s there has been an increasing concern regarding the release and accumulation of cosmetic ingredients in the environment. These compounds reach the aquatic environment by direct sources, such as bathing activities, but also by indirect sources due to industrial activities, showering, domestic washing, etc., through wastewater treatment plants at which they are not completely removed. As a result, studies have shown that cosmetic ingredients can be found not only in the water phase but also in sediments, soils and living organisms, thus affecting the flora and fauna of the aquatic environment. In this chapter, the fundamental principles of sample preparation metho…
Effects of UV filter 4-methylbenzylidene camphor during early development of Solea senegalensis Kaup, 1858
Abstract The inclusion of organic UV filters in personal care products (PCPs) has increased in recent years. 4-Methylbenzylidene camphor (4MBC) is one of the most used UV filters, and thus it is commonly found in aquatic ecosystems, with proved negative effects on aquatic organisms. Effects on early life stages of marine vertebrates are largely unknown. Therefore, the main goal of this work was to evaluate 4MBC effects on Senegalese sole (Solea Senegalensis Kaup, 1858) larvae at different levels of biological organization. S. senegalensis were exposed to increasing concentrations of 4MBC from egg stage until 96 h. Mortality, growth, malformations, behaviour and biochemical responses, includ…
Modified magnetic-based solvent-assisted dispersive solid-phase extraction: application to the determination of cortisol and cortisone in human saliva.
A modification of magnetic-based solvent-assisted dispersive solid-phase extraction (M-SA-DSPE) has been employed for the determination of the biomarkers cortisol and cortisone in saliva samples. M-SA-DSPE is based on the dispersion of the sorbent material by using a disperser solvent like in dispersive solid phase extraction (SA-DSPE) but a magnetic sorbent is used like in magnetic dispersive solid-phase extraction (M-DSPE). Thus, the magnetic sorbent containing the target analytes is retrieved using an external magnet like in M-DSPE. Finally, the analytes are desorbed into a small volume of organic solvent for the subsequent chromatographic analysis. To this regard, a M-SA-DSPE-based meth…
Reduced graphene oxide-based magnetic composite for trace determination of polycyclic aromatic hydrocarbons in cosmetics by stir bar sorptive dispersive microextraction
This work describes a sensitive and rapid analytical method for trace determination of polycyclic aromatic hydrocarbons (PAHs) in cosmetic samples. The proposed method is based on stir bar sorptive-dispersive microextraction (SBSDME). A magnetic composite made of CoFe2O4 magnetic nanoparticles embedded into reduced graphene oxide sheets is used as sorbent phase. After the extraction, the target analytes are desorbed in toluene and then analyzed by gas chromatography-mass spectrometry (GC-MS). The main parameters involved in the extraction procedure (i.e., composite amount, extraction time and desorption time) were evaluated and optimized to provide the best extraction efficiency. The method…
Sunscreen Products as Emerging Pollutants to Coastal Waters
A growing awareness of the risks associated with skin exposure to ultraviolet (UV) radiation over the past decades has led to increased use of sunscreen cosmetic products leading the introduction of new chemical compounds in the marine environment. Although coastal tourism and recreation are the largest and most rapidly growing activities in the world, the evaluation of sunscreen as source of chemicals to the coastal marine system has not been addressed. Concentrations of chemical UV filters included in the formulation of sunscreens, such as benzophehone 3 (BZ-3), 4-methylbenzylidene camphor (4-MBC), TiO2 and ZnO, are detected in nearshore waters with variable concentrations along the day a…
Use of green alternative solvents in dispersive liquid‐liquid microextraction: A review
Dispersive liquid-liquid microextraction is one of the most widely used microextraction techniques currently in the Analytical Chemistry field, mainly due to its simplicity and rapidity. The operational mode of this approach has been constantly changing since its introduction, adapting to new trends and applications. Most of these changes are related to the nature of the solvent employed for the microextraction. From the classical halogenated solvents (e.g., chloroform or dichloromethane), different alternatives have been proposed in order to obtain safer and non-pollutants microextraction applications. In this sense, low density solvents, such as alkanols, switchable hydrophobicity solvent…
Development of stir bar sorptive-dispersive microextraction mediated by magnetic nanoparticles and its analytical application to the determination of hydrophobic organic compounds in aqueous media
A novel microextraction technique combining the principles of stir bar sorptive extraction (SBSE) and dispersive micro-solid phase extraction (DμSPE) is presented. The main feature of the method is the use of a neodymium-core stirring bar physically coated with a hydrophobic magnetic nanosorbent. Depending on stirring speed, the magnetic sorbent either acts as a coating material to the stir bar, thus affording extraction alike SBSE, or as a dispersed nanosorbent medium for the collection and extraction of the target analytes, in close analogy to DμSPE. Once the stirring process is finished, the strong magnetic field of the stir bar prevails again and rapidly retrieves the dispersed MNPs. Al…
Use of Nanomaterial-Based (Micro)Extraction Techniques for the Determination of Cosmetic-Related Compounds
The high consumer demand for cosmetic products has caused the authorities and the industry to require rigorous analytical controls to assure their safety and efficacy. Thus, the determination of prohibited compounds that could be present at trace level due to unintended causes is increasingly important. Furthermore, some cosmetic ingredients can be percutaneously absorbed, further metabolized and eventually excreted or bioaccumulated. Either the parent compound and/or their metabolites can cause adverse health effects even at trace level. Moreover, due to the increasing use of cosmetics, some of their ingredients have reached the environment, where they are accumulated causing harmful effec…
Toxicity effects of the organic UV-filter 4-Methylbenzylidene camphor in zebrafish embryos
Abstract Ultraviolet (UV) filters are widely used in personal care products and due to their lipophilicity these chemicals tend to bioaccumulate in the aquatic biota. 4-Methylbenzylidene camphor (4-MBC) is one of the most used UV-filters, and it is commonly detected in freshwater fish tissues. This substance is suspected to be an endocrine disruptor due to its interaction with Hypothalamus-Pituitary-Gonadal (HPG) and HP-Thyroid (HPT)-axis. The main objective of this study was to evaluate the effects of 4-MBC on apical endpoints, biochemical markers and on genes involved in endocrine pathways in Danio rerio. Zebrafish embryos were exposed to 4-MBC (0.083–0.77 mg/l) from 0 to 96 h post-fertil…
Development of a sensitive method for determining traces of prohibited acrylamide in cosmetic products based on dispersive liquid-liquid microextraction followed by liquid chromatography-ultraviolet detection
Abstract According to the European Regulation on cosmetic products, the presence of acrylamide in these consumer products is not allowed due to its mutagenic and potentially carcinogenic effects. Despite this ban, acrylamide might be present in those cosmetic products containing acrylamide-based polymers. However, there is no analytical method for its determination in this type of matrices. Based on this, the development of analytical methods for the determination of acrylamide in cosmetic products is required to guarantee consumer safety. In this work, an analytical method for determining traces of prohibited acrylamide in cosmetic products is presented for the first time. The method is ba…
Green, rapid and simultaneous determination of ‘alternative preservatives’ in cosmetic formulations by gas chromatography-mass spectrometry
Abstract Some hydroxylated compounds commonly used in cosmetic formulations including short chain glycols, benzylic alcohols, and organic acids show antimicrobial activity, although they are not considered as preservatives according to the existing European legislation. These ‘alternative preservatives’ are not exempt of potential side-effects for cosmetics users. The aim of this work is to develop a simple and affordable analytical method useful for the simultaneous and green determination of fourteen compounds used as ‘alternative preservatives’ in cosmetic samples with different matrices. The proposed method allows a rapid sample preparation by simple dissolution or dispersion of the sam…
Expanding the application of stir bar sorptive-dispersive microextraction approach to solid matrices: Determination of ultraviolet filters in coastal sand samples
This work describes a new method for the determination of organic compounds in solid samples based on the equilibrium desorption of the analytes in an aqueous phase followed by stir bar sorptive-dispersive microextraction (SBSDME). Sand samples, contaminated with UV filters due to bathing and recreational activities, were dispersed in an aqueous medium by using a coated stir bar with CoFe2O4@oleic acid magnetic nanoparticles. The UV filters were physically desorbed from the surface of the sand particles and rapidly adsorbed on the hydrophobic coating of the nanoparticles, which were retrieved by means of their magnetism after stopping the stirring. In this manner, both preconcentration of t…
Rapid and Simple Determination of Honokiol and Magnolol in Cosmetic Products by Liquid Chromatography with Ultraviolet Detection
A rapid and simple analytical method based on liquid chromatography – ultraviolet detection has been developed and validated for the simultaneous determination of two high added-value cosmetic ingr...
Trace determination of volatile polycyclic aromatic hydrocarbons in natural waters by magnetic ionic liquid-based stir bar dispersive liquid microextraction.
In this work, a novel hybrid approach called stir bar dispersive liquid microextraction (SBDLME) that combines the advantages of stir bar sorptive extraction (SBSE) and dispersive liquid-liquid microextraction (DLLME) has been employed for the accurate and sensitive determination of ten polycyclic aromatic hydrocarbons (PAHs) in natural water samples. The extraction is carried out using a neodymium stir bar magnetically coated with a magnetic ionic liquid (MIL) as extraction device, in such a way that the MIL is dispersed into the solution at high stirring rates. Once the stirring is ceased, the MIL is magnetically retrieved onto the stir bar, and subsequently subjected to thermal desorptio…
Polydopamine-coated magnetic nanoparticles for the determination of nitro musks in environmental water samples by stir bar sorptive-dispersive microextraction.
Magnetic-based microextraction approaches have gained popularity in recent years due to the magnetic properties of the extraction phases allowing to handle them easier and more efficiently. This work describes a magnetic-based analytical method for the determination of the family of nitro musks in environmental water samples. These compounds have been of great concern due to their environmental impacts and potential health effects. The method is based on stir bar sorptive-dispersive microextraction (SBSDME) as extraction approach, prior to thermal desorption coupled to gas chromatography-mass spectrometry analysis (TD-GC-MS). For this purpose, polydopamine-coated cobalt ferrite magnetic nan…