Head Space Single Drop Micro Extraction Gas Chromatography Flame Ionization Detection (HS-SDME-GC-FID) Method for the Analysis of Common Fatty Acids.

Objectives: Post-marketing/surveillance studies show that most of the many vegetable oils that are sold with health-promoting claims or statements with high nutritional values and are beneficial against diseases are off-limits of related monographs/criteria. Defining the oil with a fast, cheap, and efficient analytical method is needed to express fatty acids in any herbal product to authenticate, trace, specify, and classify the content.The majority of the after marketing/surveillance studies shows that most of the many vegetable oils that are sold with health-promoting claims or statements with high nutritional values and are beneficial against diseases are off-limits of related monographs/criteria. Defining the oil with fast, cheap and efficient analytical method to express fatty acids in any herbal product, to authenticate, trace, specify and classify the content is needed. Materials and Methods: Here, we define a new simple tool with a headspace single drop microextraction (HS-SDME) method coupled with a gas chromatography-flame ionization detector (GC-FID) for the analysis of common fatty acids (FAs) in oils. Linolenic acid, γ-linolenic acid, and linoleic acid in olive oil, thyme oil, and fish oil were determined. Derivatization was performed with 0.2 mL of 2 mol/L KOH in methanol to transfer the FAs of oils into their methyl esters (FAMEs). Then, FAMEs were extracted using a head space single drop, which is 2.0 µL of sodium dodecyl sulfate:1-butanol (1:3, v/v) mixture. Results: The most suitable extraction condition was that 360 µL of the FAMEs, 2.0 mL vial, 0.07 g NaCl as a salting-out effect, 45 °C extraction temperature, and 35 min extraction time. The precision of the method was below 12%, with accuracy validated by the GC-FID reference method.The most suitable extraction condition was that 360 µL of the fatty acid methyl esters (FAMEs), 2.0 mL vial, 0.07 g NaCl as a salting-out effect, 45 °C extraction temperature, and 35 min extraction time. The precision of the method was below 12% with an accuracy validated by the GC-FID reference method. Conclusion: The HS-SDME can be used effectively for extracting FAs from oils for improved analysis of other FAs. The method is of direct importance and relevance for the herbal, pharmaceutical, and cosmetics industries.The HS-SDME can be used for effectively for extracting fatty acids from oils for improved analysis of other fatty acids while the method is direct importance and relevance for herbal, pharmaceutical, cosmetics industry.

Bioprospecting of Essential Oil-Bearing Plants: Rapid Screening of Volatile Organic Compounds Using Headspace Bubble-in-Drop Single-Drop Microextraction for Gas Chromatography Analysis.

Essential oils are vital constituents of oil-bearing plants. However, their screening still demands harvesting of the plant for laboratory analysis. We report herein a simple, rapid and robust headspace bubble-in-drop microextraction screening technique (BID-SPME) requiring only small amounts of plant material. The optimised method uses 0.5 g of the crushed plant leaves sample obtained in a 2 mL capped chromatography vial, heated to 55 °C and sampled with 2 µL heptadecane in a Hamilton gastight syringe equilibrated for 15 min exposed to the headspace volume. The method was applied to three plants, Pinus radiata, Tagetes minuta and Artemisia afra, which are known for their essential oil content. The method was able to extract at least 80% of the oil constituents in such abundance that they could be easily annotated using the gas chromatography-mass spectrometry (GC-MS) mass spectral libraries. The major volatile organic compounds (VOCs) detected included tagetone, terpinen-4-ol, ocimenone, caryophyllene, dihydrotagetone, terpinolene and artemisia ketone, just to mention a few, at different concentrations in different plants. Importantly, these annotated VOCs were also reported in other studies in the same and even different plants, extracted using normal steam distillation and importantly those reported in the literature for different extraction techniques.

Synergistic coupling of in-line single-drop microextraction and on-line large-volume sample stacking for capillary electrophoresis/mass spectrometry.

Single-drop microextraction (SDME) and large-volume sample stacking using an electroosmotic flow pump (LVSEP) were coupled with capillary electrophoresis/mass spectrometry (CE/MS) for sample cleanup and preconcentration. Without filtration or centrifugation of a soil sample containing debris, SDME using a pentanol acceptor drop was directly applied to the sample. After SDME, a large volume of the enriched pentanol extract was injected and further concentrated by LVSEP. For the drop formation in SDME and the sample matrix removal in LVSEP, a run buffer vial was temporarily placed to the electrospray tip, without any physical modification of the CE/MS interface. This method enabled the double preconcentration by SDME and LVSEP, achieving 600~1300-fold enrichments of anionic analytes including pesticide and herbicide compounds to provide limits of detection in the range of 0.4~0.8 ppb in soil. Graphical abstract ᅟ.

[Determination of six amphetamine-type stimulants in urine samples using electro-enhanced single drop microextraction-gas chromatography].

A method for the simultaneous determination of six amphetamine-type stimulants (ATSs) in urine by electro-enhanced single drop microextraction-gas chromatography (EE-SDME-GC) with a flame ionization detector (FID) was developed. The influences of the EE-SDME parameters on the extraction efficiencies were investigated. The 5 mL-samples at pH 7 were extracted with 2 µL dichloromethane for 3 min under an applied potential of -2.5 V. The analysis was performed on a HP-5 capillary column (30 m×0.32 mm×0.25 µm) using a flame ionization detector. The six ATSs were linear in the range of 20-1000 µg/L with correlation coefficients (r) between 0.989 and 0.997. The limits of detection (S/N=3) of the six ATSs ranged from 3.2 to 7.6 µg/L. The recoveries of the six ATSs in the spiked urine samples were 91.6%-111.2%, and the relative standard deviations were 2.9%-6.2% (n=3) at three spiked levels of 50, 100 and 500 µg/L. This method was rapid, sensitive, reliable, easily-operated and environment-friendly for the determination of the ATSs in urine samples.

Determination of essential oils composition of blanket-leaf (Stachys byzantina C. Koch.) by microwave assisted extraction coupled to headspace single-drop microextraction.

The composition of essential oils from Stachys byzantina was studied by simple method based on gas chromatography-mass spectrophotometry (GC-MS) following microwave assisted headspace single-drop microextraction (MA-HS-SDME) method. Several parameters affecting MA-HS-SDME such as sample mass, solvent volume, extraction time, microwave power and the nature of extracting solvent were optimised. The MA-HS-SDME method was compared with traditional hydrodistillation (HD) method. Within the study elaborated, thirty-eight components were extracted and identified. Compared with HD, MA-HS-SDME is an easy, rapid and efficient method for the analysis of essential oils in S. byzantina.

Direct immersion single drop micro-extraction method for multi-class pesticides analysis in mango using GC-MS.

Due the negative effects of pesticides on environment and human health, more efficient and environmentally friendly methods are needed. In this sense, a simple, fast, free from memory effects and economical direct-immersion single drop micro-extraction (SDME) method and GC-MS for multi-class pesticides determination in mango samples was developed. Sample pre-treatment using ultrasound-assisted solvent extraction and factors affecting the SDME procedure (extractant solvent, drop volume, stirring rate, ionic strength, time, pH and temperature) were optimized using factorial experimental design. This method presented high sensitive (LOD: 0.14-169.20µgkg-1), acceptable precision (RSD: 0.7-19.1%), satisfactory recovery (69-119%) and high enrichment factors (20-722). Several obtained LOQs are below the MRLs established by the European Commission; therefore, the method could be applied for pesticides determination in routing analysis and custom laboratories. Moreover, this method has shown to be suitable for determination of some of the studied pesticides in lime, melon, papaya, banana, tomato, and lettuce.

In-line coupling of single-drop microextraction with capillary electrophoresis-mass spectrometry.

Single-drop microextraction (SDME) was in-line coupled with capillary electrophoresis-mass spectrometry to provide sample cleanup and enrichment simultaneously. Since there is no outlet vial in a conventional capillary electrophoresis-electrospray ionization-mass spectrometry (CE-ESI-MS) configuration, it is not easy to hang a single drop in the capillary inlet for extraction. We overcame the difficulty of coupling SDME and CE-MS by using a temporary outlet reservoir. Basic drugs such as methamphetamine, amphetamine, phenethylamine, methoxyphenamine, and mephentermine were extracted from a basic sample solution to an acidic acceptor drop covered with a thin octanol layer formed at the capillary inlet tip. Compared to the CE-MS method in the multiple reaction monitoring (MRM) mode, the in-line SDME-CE-MS/MS technique showed 130∼150-fold enrichment in 10 min. The relative standard deviations (RSDs) of peak height ranged from 9 to 13 %. RSDs can be reduced from 4 to 6 % using mephentermine as an internal standard. We examined the pretreatment of sample with and without SDME from human urine under the full-scan mode, which confirmed that many metabolites were cleaned up by the selective extraction method of SDME. Even if the analytes from human urine were analyzed under the MRM mode used as a mass filter, there was an isobaric compound causing a disturbance to the analysis. However, in-line SDME-CE-MS/MS made it possible to perform a sample cleanup as well as sample enrichment. The research is extremely advantageous in that it is rapid, convenient, and highly sensitive for the analysis of biological samples using a commercially available instrument.

Green aspects, developments and perspectives of liquid phase microextraction techniques.

Determination of analytes at trace levels in complex samples (e.g. biological or contaminated water or soils) are often required for the environmental assessment and monitoring as well as for scientific research in the field of environmental pollution. A limited number of analytical techniques are sensitive enough for the direct determination of trace components in samples and, because of that, a preliminary step of the analyte isolation/enrichment prior to analysis is required in many cases. In this work the newest trends and innovations in liquid phase microextraction, like: single-drop microextraction (SDME), hollow fiber liquid-phase microextraction (HF-LPME), and dispersive liquid-liquid microextraction (DLLME) have been discussed, including their critical evaluation and possible application in analytical practice. The described modifications of extraction techniques deal with system miniaturization and/or automation, the use of ultrasound and physical agitation, and electrochemical methods. Particular attention was given to pro-ecological aspects therefore the possible use of novel, non-toxic extracting agents, inter alia, ionic liquids, coacervates, surfactant solutions and reverse micelles in the liquid phase microextraction techniques has been evaluated in depth. Also, new methodological solutions and the related instruments and devices for the efficient liquid phase micoextraction of analytes, which have found application at the stage of procedure prior to chromatographic determination, are presented.

Capabilities and limitations of dispersive liquid-liquid microextraction with solidification of floating organic drop for the extraction of organic pollutants from water samples.

Dispersive liquid-liquid microextraction with solidification of floating organic drop (DLLME-SFO) is one of the most interesting sample preparation techniques developed in recent years. Although several applications have been reported, the potentiality and limitations of this simple and rapid extraction technique have not been made sufficiently explicit. In this work, the extraction efficiency of DLLME-SFO for pollutants from different chemical families was determined. Studied compounds include: 10 polycyclic aromatic hydrocarbons, 5 pesticides (chlorophenoxy herbicides and DDT), 8 phenols and 6 sulfonamides, thus, covering a large range of polarity and hydrophobicity (LogKow 0-7, overall). After optimization of extraction conditions using 1-dodecanol as extractant, the procedure was applied for extraction of each family from 10-mL spiked water samples, only adjusting sample pH as required. Absolute recoveries for pollutants with LogKow 3-7 were >70% and recovery values within this group (18 compounds) were independent of structure or hydrophobicity; the precision of recovery was very acceptable (RSD<12%) and linear behavior was observed in the studied concentration range (r(2)>0.995). Extraction recoveries for pollutants with LogKow 1.46-2.8 were in the range 13-62%, directly depending on individual LogKow values; however, good linearity (r(2)>0.993) and precision (RSD<6.5%) were also demonstrated for these polar solutes, despite recovery level. DLLME-SFO with 1-dodecanol completely failed for extraction of compounds with LogKow≤1 (sulfa drugs), other more polar extraction solvents (ionic liquids) should be explored for highly hydrophilic pollutants.

Hollow-fiber liquid-phase microextraction combined with capillary electrophoresis for trace analysis of sulfonamide compounds.

A hollow-fiber liquid-phase microextraction (HF-LPME) method has been developed for the preconcentration of trace sulfonamides in water samples. Six commonly used sulfonamides including sulfamethazine (SMZ), sulfamerazine (SMR), sulfadiazine (SDZ), sulfadimethoxine (SDM), sulfamethoxazole (SMX), and sulfathiazole (STZ) were determined by CE with electrochemical detection (CE-ED) after microextraction. Several factors that affect extraction efficiency, separation, and detection were investigated. Under the optimum conditions, above sulfonamide compounds could achieve baseline separation within 35min, exhibiting a linear calibration over three orders of magnitude (r(2)≥0.998); the obtained enrichment factors were between 121 (for SDZ) and 996 (for SDM), and the LODs were in the range of 0.033-0.44ng/mL. The proposed HF-LPME/CE-ED method has been applied for the sensitive analyses of the real-world water samples with recoveries in the range of 75.1-109%.

Comprehensive overview of recent preparation and application trends of various open tubular capillary columns in separation science.

Open tubular (OT) capillary columns have been increasingly used in a variety of fields of separation science such as CEC, LC, and SPE. Especially their application in CEC has attracted a lot of attention for their outstanding separation performance. Various forms of OT stationary phase materials have been employed such as in-situ prepared polymers, molecular imprinted polymers (MIPs), brush ligands, host ligands, block copolymers, aptamers, carbon nanotubes, polysaccharides, proteins, tentacles, nanoparticles, monoliths, and polyelectrolyte multi-layers. They have been prepared either in the chemically bound format or physically adsorbed format. Sol-gel technologies and nanoparticles have been sometimes involved in their preparation. There have been also some unique miscellaneous studies, for example, adopting preferentially adsorbed mobile phase components as stationary phases. In this review, recent progresses since mostly 2007 will be critically discussed in detail with some summarized descriptions for the work before the date.