Miniaturized Extraction Techniques Research Articles

Sustainable and Biomimetic Methodology for Extraction of High-Value-Added Compounds in Almond Hulls.

Almond trees are the most cultivated nut tree in the world. The production of almonds generates large amounts of by-products, much of which goes unused. Herein, this study aimed to develop a green chemistry approach to identify and extract potentially valuable compounds from almond by-products. Initially, a screening was performed with 10 different Natural Deep Eutectic Solvents (NADESs). The mixture lactic acid/glycerol, with a molar ratio 1:1 (1:50 plant material to NADES (w/v) with 20% v/v of water) was identified as the best extraction solvent for catechin, caffeoylquinic acid, and condensed tannins in almond hulls. Subsequently, a method was optimized by a Design of Experiment (DoE) protocol using a miniaturized extraction technique, Microwave-Assisted Extraction (MAE), in conjunction with the chosen NADESs. The optimal conditions were found to be 70 °C with 15 min irradiation time. The optimal extraction conditions determined by the DoE were confirmed experimentally and compared to methods already established in the literature. With these conditions, the extraction of metabolites was 2.4 times higher, according to the increase in total peak area, than the established literature methods used. Additionally, by applying the multiparameter Analytical Greenness Metric (AGREE) and Green Analytical Process Index (GAPI) metrics, it was possible to conclude that the developed method was greener than the established literature methods as it includes various principles of green analytical chemistry.

Environmental Applications of Electromembrane Extraction: A Review.

Electromembrane extraction (EME) is a miniaturized extraction technique that has been widely used in recent years for the analysis and removal of pollutants in the environment. It is based on electrokinetic migration across a supported liquid membrane (SLM) under the influence of an external electrical field between two aqueous compartments. Based on the features of the SLM and the electrical field, EME offers quick extraction, effective sample clean-up, and good selectivity, and limits the amount of organic solvent used per sample to a few microliters. In this paper, the basic devices (membrane materials and types of organic solvents) and influencing factors of EME are first introduced, and the applications of EME in the analysis and removal of environmental inorganic ions and organic pollutants are systematically reviewed. An outlook on the future development of EME for environmental applications is also given.

Photocatalytic degradation of bisphenol-A (BPA) over titanium dioxide, and determination of its by-products by HF-LPME/GC-MS

In this work, analytical strategies were developed based on the technique of hollow fiber liquid-phase microextraction and chromatographic methods (LC-UV and GC/MS). These methods allowed the identification of the main Bisphenol-A by-products applying heterogeneous photocatalysis in water samples. BPA degradation in this study was in the order of 90%, and the conditions used in the HF-LPME were optimized through 23 factorial design (6 cm fiber length, stirring speed of 750 rpm, and an extraction time of 30 min). Using a HF-LPME/GC-MS analytical strategy, it was possible to identify six by-products of BPA photodegradation, two of which have not been reported in the literature so far. This knowledge was quite important since the degradation can lead to the formation of more toxic and persistent by-products than the BPA. With the Toxtree software, three degradation products were found to be persistent to the environment, in addition to BPA; however, in 360 minutes of reaction, chromatographic peaks of the precursors were not identified, suggesting that there may have been a total degradation of these compounds. The results showed a great application potential of a miniaturized extraction technique to extract and pre-concentrate the degradation products of emerging contaminants.

Biomonitoring of pesticides in urine by using isoamyl acetate as a sustainable extraction solvent

The protection of the health and safety of workers in the agricultural sector requires the assessment of human exposure to pesticides through biomonitoring programs. In doing this, the health and safety of laboratory analysts should be also protected through the use of analytical procedures as safe as possible. According to Green Analytical Chemistry and Green Sample Preparation principles, the use of miniaturized extraction techniques such as dispersive liquid-liquid microextraction (DLLME) should be encouraged, with the aim of limiting the consumption of chemicals (solvents and reagents) and energy, as well as the production of wastes. Moreover, safer and more environmentally friendly alternatives to petroleum-derived solvents must be found. In this regard, the effort of researchers is focused on the development/identification of sustainable solvents, some of which have been ranked according to their disposal, environmental, safety, and health features.Here, we introduce the alternative use of isoamyl acetate (“banana oil”) as sustainable extraction solvent. Compared with the trendy class of eutectic solvents (ESs), isoamyl acetate is advantageous because it is already in the liquid state, which fasters operations, and because it can be evaporated to dryness and reconstituted in a solvent compatible with the mobile chromatographic phase, which is not an option for ESs. The applicability of isoamyl acetate has been here evaluated for the first time to extract 12 pesticides of different polarities from urine matrix, by using a DLLME approach. The HPLC/MS validated method has proven to possess the sensitivity, precision and accuracy required to reliable bioanalytical methods. Its cheapness, simplicity and quickness make it an ideal sustainable choice for the screening of large numbers of samples in health monitoring programs involving people occupationally-exposed to pesticides.

Recent sample pretreatment methods for determination of selective serotonin reuptake inhibitors (SSRIs) in biological samples

Selective serotonin reuptake inhibitors (SSRIs) such as fluoxetine (FLU), sertraline (SER), paroxetine (PAR), fluvoxamine (FLV) and citalopram (CIT) have been the first treatment drugs for pregnant and breastfeeding women. Quantitative analysis of SSRIs in biological samples is extremely needed in public health and clinical practice. During the analysis, sample pretreatment is an important step that can obtain an accurate quantitative analysis of SSRIs in the complex samples. The present paper discussed the recent development of sample preparation methods for SSRI analysis. Traditional sample preparation techniques such as liquid liquid extraction (LLE) and solid phase extraction (SPE), which have been widely used in the separation of SSRIs in biological samples, were extensively presented. Moreover, the new sample preparation techniques including liquid phase microextraction (LPME), solid phase microextraction (SPME), electromembrane extraction (EME) and other miniaturized extraction techniques, which are becoming highly popular in SSRI analysis, were also critically reviewed. In this review, both the advantages and disadvantages of these sample pretreatment methods were addressed. As a summary, we prospected the challenges and promising directions for the future of sample pretreatment methods in SSRI analysis.

Recent advances in the extraction of triazine herbicides from water samples.

Pesticides are excessively used in agriculture to improve the quality of crops by eliminating the negative effects of pests. Among the different groups of pesticides, triazine pesticides are a group of compounds that contain a substituted C3 H3 N3 heterocyclic ring, and they are widely used. Triazine pesticides can be dangerous for humans as well as for the aquatic environment because of their high toxicity and endocrine disrupting effect. However, the concentration of these chemical compounds in water samples is low. Moreover, other compounds that may exist in the water samples can interfere with the determination of triazine pesticides. As a result, it is important to develop sample preparation methods that provide preconcentration of the target analyte and sufficient clean-up of the samples. Recently, a wide variety of novel microextraction and miniaturized extraction techniques (e.g., solid-phase microextraction and liquid-phase microextraction, stir bar sorptive extraction, fabric phase sorptive extraction, dispersive solid-phase extraction, and magnetic solid-phase extraction) have been developed. In this review, we aim to discuss the recent advances regarding the extraction of triazine pesticides from environmental water samples. Emphasis will be given to novel sample preparation methods and novel sorbents developed for sorbent-based extraction techniques.

Aptamer-based assays: strategies in the use of aptamers conjugated to magnetic micro- and nanobeads as recognition elements in food control

An outlook on the current status of different strategies for magnetic micro- and nanosized bead functionalization with aptamers as prominent bioreceptors is given with a focus on electrochemical and optical apta-assays, as well as on aptamer-modified magnetic bead–based miniaturized extraction techniques in food control. Critical aspects that affect interaction of aptamers with target molecules, as well as the possible side effects caused by aptamer interaction with other molecules due to non-specific binding, are discussed. Challenges concerning the real potential and limitations of aptamers as bioreceptors when facing analytical problems in food control are addressed.Graphical abstract

Polypyrrole monolithic extraction phase: From conventional to miniaturized sample preparation techniques

Monolithic polymers are described as continuous and highly porous materials. They have been gaining popularity as an effective extracting phase for some sample preparation methods, due to their variety of functionalities, such as wide pH range tolerance, good permeability, and its ability to allow changes into their surface. Polypyrrole represents an interesting alternative for the modification in extraction phases due to its well related ability to perform multiple interactions, such as acid-base, π - π, ion exchange, interactions with hydrophobic affinities or polar functional groups. Among the different sample preparation techniques, solid-phase extraction (SPE) is one of the most popular and used; a miniaturized version of SPE is the disposable pipette extraction (DPX). DPX is a recent miniaturized extraction technique that usually employing silica-based sorbents inside a pipette tip (5 or 1 mL). The present study proposes the development of a monolithic extraction phase composed by styrene divinylbenzene (1:1) modified with polypyrrole for SPE and DPX techniques. The efficiency of the material was evaluated in face of the extraction of different samples and analytes, triazine herbicides in water and dexamethasone in synthetic synovial liquid by conventional and miniaturized solid-phase extraction techniques. The extractions performed by SPE and DPX presented absolute recovery values ranging from 74.8 to 105.0%, inter-day precision ranging from 0.6 to 14.0%, and limit of quantification of 0.5 and 5.0 ng.mL−1, respectively. The DPX miniaturized method exhibited results equivalent to the methods reported in the literature for extraction of dexamethasone in synovial fluid samples. Moreover, this technique proved to be quicker and cheaper than SPE, and produced fewer residual volumes, supporting the preference for green chemistry. Monolithic polymers modified with polypyrrole presented to be a feasible alternative extraction phase for miniaturized sample preparation techniques.

Green Bioanalytical Applications of Graphene Oxide for the Extraction of Small Organic Molecules.

Bioanalysis is the scientific field of the quantitative determination of xenobiotics (e.g., drugs and their metabolites) and biotics (e.g., macromolecules) in biological matrices. The most common samples in bioanalysis include blood (i.e., serum, plasma and whole blood) and urine. However, the analysis of alternative biosamples, such as hair and nails are gaining more and more attention. The main limitations for the determination of small organic compounds in biological samples is their low concentration in these matrices, in combination with the sample complexity. Therefore, a sample preparation/analyte preconcentration step is typically required. Currently, the development of novel microextraction and miniaturized extraction techniques, as well as novel adsorbents for the analysis of biosamples, in compliance with the requirements of Green Analytical Chemistry, is in the forefront of research in analytical chemistry. Graphene oxide (GO) is undoubtedly a powerful adsorbent for sample preparation that has been successfully coupled with a plethora of green extraction techniques. GO is composed of carbon atoms in a sp2 single-atom layer of a hybrid connection, and it exhibits high surface area, as well as good mechanical and thermal stability. In this review, we aim to discuss the applications of GO and functionalized GO derivatives in microextraction and miniaturized extraction techniques for the determination of small organic molecules in biological samples.

Metal-Organic Frameworks in Bioanalysis: Extraction of Small Organic Molecules

The quantitative determination of xenobiotic compounds, as well as biotics in biological matrices, is generally described with the term bioanalysis. Due to the complexity of biofluids, in combination with the low concentration of the small molecules, their determination in biological matrices is a challenging procedure. Apart from the conventional solid-phase extraction, liquid-liquid extraction, protein precipitation, and direct injection approaches, nowadays, a plethora of microextraction and miniaturized extraction techniques have been reported. Furthermore, the development and evaluation of novel extraction adsorbents for sample preparation has become a popular research field. Metal-organic frameworks (MOFs) are novel materials composed of metal ions or clusters in coordination with organic linkers. Unequivocally, MOFs are gaining more and more attention in analytical chemistry due to their superior properties, including high surface area and tunability of pore size and functionality. This review discusses the utilization of MOFs in the sample preparation of biological samples for the green extraction of small organic molecules. Their common preparation and characterization strategies are discussed, while emphasis is given to their applications for green sample preparation.

Solid-Liquid-Liquid Microextraction (μSLLE) Method for Determining Persistent Pollutants in Microplastics

Ongoing pollution of the marine environment requires quick and reasonably priced analytical techniques that allow routine checking of the concentrations of persistent organic pollutants (POPs) found in different samples and, in particular, coastal samples. Miniaturized extraction techniques enable us to analyze samples more quickly and cheaply. These methodologies are highly effective for analysis of liquid samples, but not for solid samples, and even less so for microplastic pollutant analyses. A miniaturized solid-liquid-liquid extraction technique (μSLLE) has been developed to extract, pre-concentrate, and analyze up to 27 POPs from marine microplastics, using a quick methodology which does not require drying of the extract for its preconcentration. Target pollutants were analyzed using single quadrupole gas chromatography with mass spectrometry (GC-MS). The method has been optimized and validated, and was applied to different marine microplastic samples collected on the islands of Gran Canaria and Fuerteventura (Canary Islands, Spain).

Green Miniaturized Extraction and Microextraction of Polycyclic Aromatic Hydrocarbons from Foods and Beverages

Background: Polycyclic aromatic hydrocarbons (PAHs) are common environmental contaminants consisting of two or more fused benzene rings. PAHs can be introduced into foodstuffs through different ways, such as smoking, roasting and grilling for meat and fish, absorption from the environment for edible oils, chemical treatment of crops for plant-based products, or contamination through packaging during storage. Due to the low concentrations of PAHs in foodstuffs, a clean-up and preconcentration sample preparation technique is of high importance. Until recently, solid-phase and liquid-liquid extraction were the most popular sample preparation techniques for the extraction of PAHs from food matrices. However, due to the fundamental drawbacks of those extraction procedures, a plethora of novel methods, including micro-extraction techniques and miniaturized extraction techniques, have been developed. Moreover, a wide variety of novel adsorbent materials (e.g., metal-organic frameworks, carbon-based materials, etc.) have been synthesized and applied for PAHs’ extraction. Objective: This review aims to discuss recent advances in the extraction techniques of PAHs from food samples, utilizing novel sample preparation approaches and adsorbents. Conclusion: Compared with the traditional sample preparation techniques, the herein discussed green miniaturized extraction and microextraction techniques offer multiple benefits, including simplicity, reduced sample preparation time, as well as reduced consumption of organic solvents.

Green sample preparation of alternative biosamples in forensic toxicology

Forensic toxicology is the scientific field that is associated with death investigations, matters involving drugs determination, sports doping etc. In forensic toxicology, reliable qualitative and quantitative toxicological analysis of a wide variety of drugs with different chemical properties (e.g., amphetamines, benzodiazepines, cannabis and opiates) is required. Alternative biosamples including hair, nails, saliva, sweat, cerebrospinal fluid and dried blood spots can be efficiently used in forensic toxicology to provide necessary or additional information. These samples exhibit certain benefits towards conventional blood and urine samples, such as ease in collection, stability, and provision of useful information for a long time period. Gas chromatography and liquid chromatography coupled with mass detectors or tandem mass detectors are the most powerful instrumentations for the determination of analytes of interest in forensic toxicology. Sample preparation is required to make the analyte compatible with these instrumentations, to remove matrix interferences and to preconcentrate them. For this purpose, solid-phase extraction (SPE) and liquid-liquid extraction (LLE) have been widely used. However, since the development of green analytical chemistry that emerged from green chemistry, a plethora of microextraction and miniaturized extraction techniques have been developed. In this review article we aim to discuss the green sample preparation techniques of alternative biosamples in forensic toxicology reported during the last 10 years.

Greenness of magnetic nanomaterials in miniaturized extraction techniques: A review

Green analytical chemistry principles should be followed, as much as possible, and particularly during the development of analytical sample preparation methods. In the past few years, outstanding materials such as ionic liquids, metal-organic frameworks, carbonaceous materials, molecularly imprinted materials, and many others, have been introduced in a wide variety of miniaturized techniques in order to reduce the amount of solvents and sorbents required during the analytical sample preparation step while pursuing more efficient extraction methods. Among them, magnetic nanomaterials (MNMs) have gained special attention due to their versatile properties. Mainly, their ability to be separated from the sample matrix using an external magnetic field (thus enormously simplifying the entire process) and their easy combination with other materials, which implies the inclusion of a countless number of different functionalities, highly specific in some cases. Therefore, MNMs can be used as sorbents or as magnetic support for other materials which do not have magnetic properties, the latter permiting their combination with novel materials. The greenness of these magnetic sorbents in miniaturized extractions techniques is generally demonstrated in terms of their ease of separation and amount of sorbent required, while the nature of the material itself is left unnoticed. However, the synthesis of MNMs is not always as green as their applications, and the resulting MNMs are not always as safe as desired. Is the analytical sample preparation field ready for using green magnetic nanomaterials? This review offers an overview, from a green analytical chemistry perspective, of the current state of the use of MNMs as sorbents in microextraction strategies, their preparation, and the analytical performance offered, together with a critical discussion on where efforts should go.

Recent Advances in the Extraction of Polycyclic Aromatic Hydrocarbons from Environmental Samples.

Polycyclic aromatic hydrocarbons (PAHs) comprise a group of chemical compounds consisting of two or more fused benzene rings. PAHs exhibit hydrophobicity and low water solubility, while some of their members are toxic substances resistant to degradation. Due to their low levels in environmental matrices, a preconcentration step is usually required for their determination. Nowadays, there is a wide variety of sample preparation techniques, including micro-extraction techniques (e.g., solid-phase microextraction and liquid phase microextraction) and miniaturized extraction techniques (e.g., dispersive solid-phase extraction, magnetic solid-phase extraction, stir bar sorptive extraction, fabric phase sorptive extraction etc.). Compared to the conventional sample preparation techniques, these novel techniques show some benefits, including reduced organic solvent consumption, while they are time and cost efficient. A plethora of adsorbents, such as metal-organic frameworks, carbon-based materials and molecularly imprinted polymers, have been successfully coupled with a wide variety of extraction techniques. This review focuses on the recent advances in the extraction techniques of PAHs from environmental matrices, utilizing novel sample preparation approaches and adsorbents.

Simplified analytical methodology for glucosinolate hydrolysis products: a miniaturized extraction technique and multivariate optimization

Miniaturized extraction techniques are one of the most significant advances in analytical chemistry today.

Analysis of Dyes in Cosmetics: Challenges and Recent Developments

Colour plays a decisive role in the marketing of a cosmetic product. Among thousands of substances used to colour, synthetic dyes are the most widespread in the industry. Their potential secondary effects on human health and different regulatory requirements for their use between the main world markets make analytical control necessary to guarantee the safety of a cosmetic product. However, methodologies for the determination of dyes in cosmetics are scarce with respect to those reported for other cosmetic ingredients such as preservatives or ultraviolet UV filters. In addition, most of the existing methods just consider a part of the total of dyes regulated. On the other hand, many methods have been developed for matrices different than cosmetics such as foodstuff, beverages or wastewater. The current paper reviews the recent developments in analytical methodologies for the control of synthetic dyes in cosmetics proposed in the international scientific literature in the last 10 years (2008–2018). A trend towards the use of miniaturized extraction techniques is evidenced. Due to the hydrophilic nature of dyes, liquid chromatography is the most usual choice in combination with absorbance detectors and, more recently, with mass spectrometry.

A new and fast strategy based on semiautomatic microextraction by packed sorbent followed by ultra high performance liquid chromatography for the analysis of drugs and their metabolites in human urine.

A novel analytical approach has been developed for the determination of selected drugs (milrinone, enalapril, carvedilol, spironolactone, acenocumarol, ticlopidine, cilazapril) and their metabolites (2-oxoticlopidine, cilazaprilat, canrenone, 5'-hydroxycarvedilol, O-desmethyl-carvedilol, enalaprilat) in human urine, based on aminiaturized extraction technique; semiautomatic microextraction by packed sorbent, using a new digitally controlled syringe, followed by ultra high pressure liquid chromatography separation combined with UV detection. During method optimization, the extraction parameters as the type of sorbent material, type and volume of elution solution, number of extraction cycles, volume and pH of sample, type and volume of washing solution were studied. The chromatographic separation of the target analytes was performed with a core-shell analytical column using 0.05% trifluoroacetic acid in water and acetonitrile in gradient elution mode. The limits of quantification ranged from 0.016 to 0.045μg/mL. Under the optimized conditions, extraction efficiency was higher than 70.1% for drugs and their metabolites. Due to its simplicity and speed, this method was successfully applied to the quantitation of selected compounds in urine samples.

Supercritical Fluid Technology in Analytical Chemistry - Review

This review provides an updated discussion on the recent developments and applications of supercritical fluid technology in analytical chemistry. Supercritical mediums are usually used for extraction and separation of various analytes in analytical science. Although, this technology is used for chromatographic aims in the analysis of various samples the main application domain of supercritical fluids is in extraction process. SFE is suitable for recovery of various analytes, especially non-polar organic compounds, from different matrices. However, via some modifications or by the aid of modifiers or a chelating agent, this technique could be successfully applied in the extraction of polar or even ionic analytes. The range of analytes extracted via SFE is wide and mostly includes food and pharmaceutical samples, pollutants extraction and metal cation extraction. The aim of this paper is to review, from analytical chemistry standpoint, recent advances in the use of SC-CO2 for the extraction and separation of analytes. At the same time, a critical assessment will be made of the advantages of SCF technology in comparison with traditional methods. Special emphasis will be given to online coupling of SFE method with chromatographic techniques and FT-IR spectroscopy that make possible the extraction and separation of various analytes from different matrices in order to produce novel analytical techniques. The potentials, advantages, shortcomings, and prospects in employment of supercritical fluids for separation and extraction of various analytes are also considered. The efficiencies of SFE for the extraction of various analytes from solid and aqueous samples are compared to traditional methods such as Soxhlet extraction. Supercritical fluid extraction due to various reasons such as its greenness, rapidity and high efficiency are widely used an alternative to conventional solvent-based extraction methods. Also, SFE can be as an automated and miniaturized extraction technique, since it reduces the amounts of required samples considerably. SFE avoids multi-steps of conventional methods (such as partitioning, clean-up, evaporation) and hence it can reduce the uncertainty in the results. Furthermore, SFE reduces analysis times and is less laborintensive. Keywords: Supercritical fluids, chromatographic methods, cleanup, extraction, food analysis, pollutants.

Three-phase hollow fiber liquid-phase microextraction of organophosphorous nerve agent degradation products from complex samples

Degradation products of chemical warfare agents are considered as important environmental and biological markers of chemical attacks. Alkyl methylphosphonic acids (AMPAs), resulting from the fast hydrolysis of nerve agents, such as sarin and soman, and the methylphosphonic acid (MPA), final degradation product of AMPAs, were determined from complex matrices by using an emergent and miniaturized extraction technique, the hollow fiber liquid-phase microextraction (HF-LPME), before their analysis by liquid chromatography coupled to mass spectrometry (LC–MS). After studying different conditions of separation in the reversed phase LC–MS analysis, the sample treatment method was set up.The three-phase HF-LPME was carried out by using a porous polypropylene (PP) hollow fiber impregnated with 1-octanol that separates the donor and acceptor aqueous media. Various extraction parameters were evaluated such as the volume of the sample, the effect of the pH and the salt addition to the sample, the pH of the acceptor phase, the extraction temperature, the stirring speed of the sample, the immersion time in the organic solvent and the time of extraction. The optimum conditions were applied to the determination of MPA and five AMPAs in real samples, such as surface waters and urine. Compounds were extracted from a 3mL acidified sample into only 6μL of alkaline water without any other pretreatment of the complex matrices. Enrichment factors (EFs) higher than 170 were obtained for three less polar AMPAs. Limits of quantification (LOQs) in the 0.013–5.3ngmL−1 range were obtained after microextraction of AMPAs from river water and in the range of 0.056–4.8ngmL−1 from urine samples with RSD values between 1 and 9%.