Capsule phase microextraction of six bisphenols from human breast milk using a monolithic polyethylene glycol sorbent-based platform prior to high performance liquid chromatography-photo-diode array detection determination.

The determination of bisphenols in human breast milk is a matter of ongoing interest since it reveals the exposure levels in both lactating mothers, fetuses, and infants. Herein, capsule phase microextraction (CPME) is applied for the first time for the extraction of a mixture of bisphenols from human breast milk followed by their subsequent determination by high-performance liquid chromatography-photodiode array detection (HPLC-DAD). CPME is a recently introduced as an advanced micro preparative technique that meets the principles of Green Analytical Chemistry. Moreover, it integrates filtration, extraction and stirring mechanism into one single device, a composite attribute that allows selective extraction of analytes without any sample cleanup and facilitates faster extraction kinetics, resulting in enhancing the performance of the equilibrium-based extraction techniques that ensure better reproducibility and operational simplicity. Among four tested CPME devices, the sol-gel poly(ethylene glycol) capsules showed the best extraction efficiency. Critical factors of the extraction performance were investigated and optimized. The developed CPME-HPLC-PDA method was validated. Limits of detection and quantification were 7.58 ng/mL and 25 ng/mL, respectively. Relative recoveries were estimated between 89.7 and 110.5%, while the RSD values were <11% in all cases. CPME is poised to be a useful tool both for routine bioanalysis and research purposes.

Determination of phenolic compounds in human saliva after oral administration of red wine by high performance liquid chromatography.

Red wine is a relevant source of bioactive compounds, which contribute to its antioxidant activity and other beneficial advantages for human health. However, the bioavailability of phenols in humans is not well understood, and the inter-individual variability in the production of phenolic compounds has not been comprehensively assessed to date. The present work describes a new method for the extraction and analysis of phenolic compounds including gallic acid (Gal), vanillic acid (Van), caffeic acid (Caf), syringic acid (Sir); (-)-epicatechin (Epi); p-coumaric acid (Cum) and resveratrol (Rsv) in human saliva samples. The target analytes were extracted using Fabric Phase Sorptive Extraction (FPSE), and subsequently analysed by high-performance liquid chromatography (HPLC) coupled with photodiode array detector (PDA). Chromatographic separation was achieved using a Symmetry C18 RP column in gradient elution mode, with methanol and phosphate buffer as the mobile phases. The linearity (intercept, slope, and determination coefficient) was evaluated in the range from 1 to 50 µg/mL. The limit of quantification (LOQ) was 1 µg/mL (LLOQ ≥0.8 µg/mL), whereas limit of detection was 0.25 µg/mL. The intra and inter-day RSD% and BIAS% values were less than± 15%. The analytical performances were further tested on human saliva collected from healthy volunteers after administering red wine. To the best of our knowledge, this is the first FPSE procedure for the analysis of phenols in saliva, using a non-invasive and easy to perform sample collection protocol. The proposed fast and inexpensive approach can be deployed as a reliable tool to study other biological matrices to proliferate understanding of these compounds distribution in human body.

Rapid exposure monitoring of six bisphenols and diethylstilbestrol in human urine using fabric phase sorptive extraction followed by high performance liquid chromatography - photodiode array analysis.

A novel fabric phase sorptive extraction protocol is developed for rapid exposure monitoring of six bisphenol analogues, including bisphenol A, bisphenol S, bisphenol F, bisphenol E, bisphenol B, bisphenol C, and diethylstilbestrol (DES) from human urine prior to high-performance liquid chromatography-photodiode array analysis. FPSE sample pretreatment protocol ensures the harmonization of the proposed method with the principles of Green Analytical Chemistry (GAC). Among eighteen evaluated FPSE membranes, sol-gel poly (ethylene glycol) (PEG) coated cellulose FPSE membrane resulted in the most efficient extraction. This polar FPSE membrane effectively exploits a number of advantageous features inherent to FPSE including sponge-like porous architecture of the sol-gel sorbent coating, favorable surface chemistry, flexibility and built-in permeability of cellulose fabric substrate, high primary contact surface area for rapid sorbent-analyte interaction, expanded pH, solvent and thermal stability as well as reusability of the FPSE membrane. Optimization was centered on the evaluation of critical parameters, namely the size of the FPSE membrane, the elution solvent mixture, the volume of the sample, the extraction time, the elution time, the kind of the external agitation mechanical stimulus, the ionic strength and the pH of the sample. The chromatographic separation was achieved on a Spherisorb C18 column and a gradient elution program with mobile phase consisted of 0.05 ammonium acetate solution and acetonitrile. The total analysis time was 17.4 min. The developed method was validated in terms of linearity, sensitivity, selectivity, precision, accuracy, stability, and ruggedness. The limits of detection and quantification varied from 0.26-0.62 ng/mL and 0.8-1.9 ng/mL, respectively. The relative recoveries were calculated between 90.6 and 108.8%, while the RSD values were <10% in all cases. The effectiveness of the proposed method was confirmed by its successful implementation in the bioanalysis of real urine samples.

Fast off-line FPSE-HPLC-PDA determination of six NSAIDs in saliva samples.

A fast off-line FPSE-HPLC-PDA method has been reported that allows simultaneous clean up and determination of six non-steroidal anti-inflammatory drugs (NSAIDs) in saliva samples from healthy volunteers. Particularly, furprofen, indoprofen, ketoprofen, fenbufen, flurbiprofen, and ibuprofen were chromatographically resolved. Benzyl paraben was chosen as the internal standard (BzPB, IS). These target compounds were successfully extracted from human saliva using fabric phase sorptive extraction (FPSE) and then analysed in the liquid chromatographic system by means of a short analytical column (Symmetry C18, 75 × 4.6 mm, 3.5 µm) using acetonitrile (AcN) and phosphate buffer (PBS, 30 mM; pH = 2.5) as the mobile phases. The method, validated through the calculation of all analytical parameters in accordance of International Guidelines, was applied to real saliva sample analysis collected from informed volunteers. The proposed approach that included the use of sol-gel polytetrahydrofuran (sol-gel PTHF) sorbent immobilized on cellulose support and C18 stationary phase used in HPLC, showed high potential as a fast tool for future clinical and forensic applications. The herein reported results encourage potential future application of FPSE in the forensic field. Furthermore, the FPSE membrane was tested in dried saliva spot mode (DSS) in order to check its potential use as a sampling device, also for forensic applications.

Biofluid sampler: A new gateway for mail-in-analysis of whole blood samples.

The current study reports the development of a novel biofluid sampler (BFS) which is capable of sampling and sample preparation of whole blood without converting it into plasma or serum. The sampler can retain a whole blood sample from 10 to 1000 µL. Although the device shares the same working principle of dried blood spot (DBS) cards, it eliminates most of the technological shortcomings of DBS cards such as low maximum sample volume (~50 µL), sample inhomogeneity due to haematocrit, and poor physical adsorption driven analyte retention by incorporating sol-gel derived high efficiency, multi-functional sorbents on cellulose fabric substrate. The performance of BFS was tested via "Mail-in-Analysis" using three non-steroidal anti-inflammatory drugs (NSAIDs, ketoprofen, carprofen and diclofenac) as the test compounds. Human whole blood samples were fortified with the test compounds and sampled on conventional DBS cards and biofluid samplers (BFSs) in the USA. After drying the blood samples at room temperature, the samples were shipped to Italy for chromatographic analysis. The analytes were back-extracted from the DBS cards and BFSs using methanol and subsequently analysed using a short Symmetry C18 column (75 × 4.6 mm, 3.5 µm). Acetonitrile (ACN) and PBS (30 mM; pH = 2.5) were used as the mobile phases and the elution was performed under isocratic conditions. Compared to the classical dried blood spot cards (DBS), BFSs offer better performance in retaining the selected NSAIDs under conventional postal shipment. By substantially expanding the sampling capacity, eliminating most of the shortcomings of classical DBS cards and exploiting the better materials properties of sol-gel based functional sorbents, BFSs offer a new and profoundly simplified approach for whole blood sampling and analysis and is expected to change the current practice of blood analysis, allowing accurate quantitative analyses either in a local laboratory (on site) or using mail-in-analysis (off site) without compromising the quality of bioanalytical data.

Fabric phase sorptive extraction followed by ultra-performance liquid chromatography-tandem mass spectrometry for the determination of fungicides and insecticides in wine.

In this work, fabric phase sorptive extraction (FPSE) is investigated for the extraction and preconcentration of ultra-trace level residues of fungicides (19 compounds) and insecticides (3 species) in wine samples. Subsequently, the preconcentrated analytes are selectively determined using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Parameters affecting the efficiency and repeatability of the extraction are evaluated in depth; moreover, the proposed method is characterized in terms of linear response range, trueness, precision and limits of quantification (LOQs). The set-up of the extraction process and the type of coating were the variables exerting the most prominent effects in the repeatability and the yield of the extraction, respectively. Under optimized conditions, samples (10 mL of wine diluted with the same volume of ultrapure water) were extracted with a small amount of cellulose fabric (3 discs with 4 mm of diameter: total surface 0.38 cm2) coated with a sol-gel polyethylene glycol sorbent (sorbent amount 3.3 mg), immersed in the diluted sample, without being in direct contact with the PTFE covered magnetic stir bar. Following the overnight extraction step, analytes were quantitatively recovered using only 0.3 mL of an ACN-MeOH (80:20) mixture. Under equilibrium sampling conditions, the linear response range of the method varied from 0.2 to 200 ng mL-1, with limits of quantification (LOQs) between 0.03 and 0.3 ng mL-1. Relative recoveries ranged from 77 ± 6% to 118 ± 4%, and from 87 ± 4% to 121 ± 6% for red and white wines, respectively. Application of the optimized method to commercial wines demonstrated the existence of up to 9 out of 22 investigated compounds in the same wine sample. The compound identified at the highest concentration was iprovalicarb (IPR), with a value of 130 ± 9 ng mL-1 in a commercial white wine.

Fabric phase sorptive extraction as a reliable tool for rapid screening and detection of freshness markers in oranges.

A simple, fast and sensitive analyte extraction method based on fabric phase sorptive extraction (FPSE) followed by gas chromatography-mass spectrometry (GC-MS) and ultra-performance liquid chromatography-quadrupole time of flight mass spectrometry (UPLC-QTOF-MS) analysis was developed for the analysis of 12 volatile compounds that represent most of the principal chemical families possessing different polarities and volatilities. Five FPSE media coated with different sol-gel sorbent chemistries having different polarities and selectivities were studied: long chain poly(dimethylsiloxane) (PDMS), short chain poly(tetrahydrofuran) (PTHF), Carbowax 20M (CW20M), short chain poly(dimethyl siloxane) (SC PDMS) and polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer (PEG-PPG-PEG). CW20M coated FPSE media was found to be the most efficient extraction media for the analytes of interest in the intended study. The developed methodology was applied to the analysis of orange juice obtained from fresh oranges and oranges after storing at 5°C for two months in order to identify the best chemical markers, both volatiles and non-volatiles, attributed to the freshness of orange. For this purpose, aliquots of the same juice extracts were analysed by GC-MS as well as by UPLC-QTOF-MS. Monoterpenes and terpenoids, such as terpinene, citronellal or estragole were among the volatile compounds that endured the biggest decrease after the extended storage period. Three non-volatile compounds including one amide (subaphyllin) and two flavanoids (tangeretin and nobiletin) also showed a clear decrease in signal intensity (>70%) after orange stored for two months.

Fabric phase sorptive extraction: An innovative sample preparation approach applied to the analysis of specific migration from food packaging.

Additives added to food packaging materials can migrate to food in contact with them during storage and shelf life. A novel simple, fast and sensitive analyte extraction method based on fabric phase sorptive extraction (FPSE), followed by analysis using ultra-high performance liquid chromatography and mass spectrometry detection (UPLC-MS) was applied to the analysis of 18 common non-volatile plastic additives. Three FPSE media coated with different sol-gel sorbents characterized with different polarities including sol-gel poly(dimethylsiloxane), sol-gel poly(ethylene glycol) and sol-gel poly(tetrahydrofuran) were studied. All three FPSE media showed very satisfactory results. In general, compounds with low logP values seemed to have higher enrichment factors (EFs), especially with poly(tetrahydrofuran) and poly(ethylene glycol) media. For compounds with high logP values, the use of sol-gel poly(dimethylsiloxane) improved the enrichment capacity. Sample preparation time was optimized at 20 min for sample extraction and 10 min for solvent desorption. Acetonitrile was selected as desorption solvent since recoveries were over 70% for 13 out of 18 selected compounds in all FPSE media. The best extraction recovery values were obtained when compounds were dissolved in aqueous acetic acid solution (3%), where 17 out of 18 compounds showed improvement in their signal intensity after FPSE extraction and 10 obtained enrichment factors above 3 for all the tested FPSE media. When FPSE extracts were concentrated under nitrogen, 11 out of 18 compounds reached EFs values above 100.

An automated flow injection system for metal determination by flame atomic absorption spectrometry involving on-line fabric disk sorptive extraction technique.

A novel flow injection-fabric disk sorptive extraction (FI-FDSE) system was developed for automated determination of trace metals. The platform was based on a minicolumn packed with sol-gel coated fabric media in the form of disks, incorporated into an on-line solid-phase extraction system, coupled with flame atomic absorption spectrometry (FAAS). This configuration provides minor backpressure, resulting in high loading flow rates and shorter analytical cycles. The potentials of this technique were demonstrated for trace lead and cadmium determination in environmental water samples. The applicability of different sol-gel coated FPSE media was investigated. The on-line formed complex of metal with ammonium pyrrolidine dithiocarbamate (APDC) was retained onto the fabric surface and methyl isobutyl ketone (MIBK) was used to elute the analytes prior to atomization. For 90s preconcentration time, enrichment factors of 140 and 38 and detection limits (3σ) of 1.8 and 0.4µgL(-1) were achieved for lead and cadmium determination, respectively, with a sampling frequency of 30h(-1). The accuracy of the proposed method was estimated by analyzing standard reference materials and spiked water samples.

The scientific foundation and efficacy of the use of canines as chemical detectors for explosives.

This article reviews the use of dogs as chemical detectors, and the scientific foundation and available information on the reliability of explosive detector dogs, including a comparison with analytical instrumental techniques. Compositions of common military and industrial explosives are described, including relative vapor pressures of common explosives and constituent odor signature chemicals. Examples of active volatile odor signature chemicals from parent explosive chemicals are discussed as well as the need for additional studies. The specific example of odor chemicals from the high explosive composition C-4 studied by solid phase microextraction indicates that the volatile odor chemicals 2-ethyl-1-hexanol and cyclohexanone are available in the headspace; whereas, the active chemical cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX) is not. A detailed comparison between instrumental detection methods and detector dogs shows aspects for which instrumental methods have advantages, a comparable number of aspects for which detector dogs have advantages, as well as additional aspects where there are no clear advantages. Overall, detector dogs still represent the fastest, most versatile, reliable real-time explosive detection device available. Instrumental methods, while they continue to improve, generally suffer from a lack of efficient sampling systems, selectivity problems in the presence of interfering odor chemicals and limited mobility/tracking ability.

Application of solid-phase microextraction to the recovery of explosives and ignitable liquid residues from forensic specimens.

A current review of the application of solid-phase microextraction (SPME) to the analysis of ignitable liquids and explosive residues is presented along with experimental results demonstrating the relative effects of controllable variables. Variables discussed include fiber chemistry, adsorption and desorption temperatures, extraction and desorption times, fiber sampling placement (direct, headspace, and partial headspace) and matrix effects, including water content. SPME is shown to be an inexpensive, rapid and sensitive method for the analysis of ignitable liquids and high explosives residues from solid debris samples and from aqueous samples. Explosives are readily detected at parts per trillion concentrations and ignitable liquids are reproducibly detected at levels below those using conventional methods.

The use of solid-phase microextraction--gas chromatography in forensic analysis.

A thorough review of the application of solid-phase microextraction (SPME) combined with gas chromatography for the analysis of forensic specimens is presented, including experimental results for several recent applications. The SPME applications covered in this comprehensive review include ignitable liquid residues (also referred to as accelerants), explosive traces, drugs and poisons from biological specimens, and other forensic applications. Recently developed SPME methods are also presented, including the analysis of ignitable liquid residues on human skin, odor signatures, and several drug applications such as free-fraction antipsychotic drug levels, blood alcohol casework, drink-tampering analysis, and gamma-hydroxybutyrate identification without the need for derivatization. SPME is shown to be an inexpensive, rapid, and sensitive method for the analysis of a variety of forensic specimens.

The detection and analysis of ignitable liquid residues extracted from human skin using SPME/GC.

A simple, fast, inexpensive, and sensitive technique for the detection and identification of flammable or combustible liquid residues on the skin of arson suspects is presented. The use of solid phase microextraction (SPME) for the analysis of ignitable liquid residues has been demonstrated and it is shown in this work that this technique is effective in extracting these liquid residues at extremely low quantities. Microliter quantities of controlled spikes of gasoline, diesel fuel, and charcoal lighter fluid were deposited on the hands of a volunteer and extracted after several time intervals. The SPME technique can recover very small amounts of liquid deposits on skin up to 3.5 h after exposure, depending on the class of the ignitable liquid residue used.

Gas chromatographic study of complexing in the system hydrazoic acid-tributyl phosphate-nitric acid-uranyl nitrate.

Elution gas chromatography has been used to study complexing of hydrazoic acid with tributyl phosphate (TBP) in hexadecane solution in the presence of nitric acid and/or uranyl nitrate. The study covered the temperature range 298-338 K, with concentrations of either additive up to 0.41 mol dm(-3). The results for hydrazoic acid elution at infinite dilution establish (a) that stoichiometry of the TBP-HNO3 complex is 1:1 and (b) that both 2:1 and 1:1 TBP-UO2(NO3)2 complexes co-exist in the system, the latter increasing in amount as the temperature is raised. Both HNO3 and UO2(NO3)2 act simply to reduce the amount of TBP free to form the 1:1 TBP-HN3 complex. Stability constants for the equilibrium UO2(NO3)2 TBP+TBP4<-->UO2(NO3)2 x 2TBP are presented.

Discrimination of glass sources using elemental composition and refractive index: development of predictive models.

Refractive index and metal ion concentrations (Al, Ba, Ca, Fe, Mg, Mn, Sr, Ti and Zr) were determined for four product-use categories: headlamp glass; container glass, non-vehicle window float glass, and vehicle float glass. Linear discriminant modelling using these data allowed differentiation of the four glass types but further discrimination was not possible within a product-use category. For this specific set of glasses, the concentrations of a number of metal ions were found to be correlated in some cases. This precluded the use of traditional probability calculations in using elemental composition data for interpretation of glass evidence. Alternative approaches to glass data interpretation are suggested.

The gas-liquid chromatographic stationary phase properties of liquid organic salts: Anomalous selectivity variation when employing the Rohrschneider/McReynolds system.

The liquid organic salts studied here have wide stable liquid temperature ranges and act as efficient, highly selective gas-liquid chromatographic stationary phases. The effect of carbon number on the gas liquid chromatographic stationary phase properties of this series of tetra-n-butylammonium n-alkylsulfonate salts was evaluated by the well-known Rohrschneider/McReynolds system. Several problems arose when attempting to characterize these polar liquid organic salts employing this system. The specific retention volumes for the polar selectivity probes were generally not affected by an increase in the carbon number for the series studied here. However, the specific retention volumes for the n-alkane retention index markers increased dramatically as the anion carbon number was increased. The overall effect was a net decrease in the calculated McReynolds constants with increasing carbon number, although the true selectivity of the different stationary phases remained constant. Additionally, the specific retention volumes of the basic test probe, pyridine, showed large erratic variations and, in some cases, was not recovered from the columns. The results suggest the possibility of on-column chemical reactions occurring with some of these salts, and an alternative test probe, 2,6-dimethylpyridine (lutidine) is proposed to eliminate this problem. As McReynolds constants are presently the most commonly used parameters for predicting retention and gas chromatographic stationary phase selection, it is important that workers are aware of the inherent limitations of this scheme.