Standard Water Generating Vials for Lipophilic Compounds.

The study of non-polar compounds in aqueous environments has always been challenging due to their poor solubility in aqueous media. The low affinity of non-polar compounds toward polar solutions facilitates their attachment to glassware, which results in unstable sample concentrations. To address this challenge, and to enable the preparation of a stable mixture of hydrophobic compounds in an aquatic environment, we introduce an in-vial standard water generating system consisting of a vial containing appropriate aqueous solution and a polydimethylsiloxane thin film spiked with target compounds. In this system, a solution with a stable analyte concentration is attained once equilibrium between the thin-film and aqueous solution has been achieved. The developed standard water system was studied using endocannabinoids and phospholipids as model hydrophobic compounds of biological importance, with results indicating that the concentration of hydrophobic compounds in water can remain stable over multiple days. The results also showed that analytes released from the thin film can compensate for analyte loss due to extractions with solid-phase microextraction fibers, thereby re-establishing equilibrium. Thus, the vial is suitable for the repeatable generation of non-polar standards for routine analysis and quality control. The results of this work show that the developed system is stable and reproducible and therefore appropriate for studies requiring the measurement of free concentrations and accurate quantification.

Effect of household air pollutants on the composition of exhaled breath characterized by solid-phase microextraction and needle-trap devices.

Exposure to household air pollutants is becoming a serious environmental health risk. Various methods can be applied to assess humans' exposure status to indoor pollutants, with breath monitoring being among the best options. Breath sampling is fast and non-invasive, and contains compounds that can be used as markers for evaluating exposure length and estimating internal concentrations of pollutants. However, the distribution of compounds between gas and droplets in breath samples represents one of the key challenges associated with this analytical method. In this work, a needle-trap device (NTD) was prepared by packing the needle with a porous filter, divinyl benzene, and Carboxen to enable the exhaustive capture of both droplet-bound and gaseous components. Furthermore, fiber-based solid-phase microextraction (SPME) was also applied to extract compounds from only the gas phase to distinguish this portion of analytes from the total concentration in the sample. Dynamic, real-time breath sampling was enabled via a new sampling tube equipped with 2 one-way valves, which was specially designed for this work. Both methods provided satisfactory reproducibility, repeatability, and sensitivity, with detection limits as low as 0.05 ng mL-1. To investigate the real-world applicability of the proposed devices, breath samples were obtained from volunteers who had been exposed to candle and incense smoke and aerosol sprays, or had smoked cannabis. The results revealed the high concentration of organic air pollutants in inhaled air (maximum of 215 ng mL-1) and exhaled breath (maximum of 14.4 ng mL-1) and a correlation between the components in inhaled air and exhaled breath. Significantly, the findings further revealed that the developed NTD has enhanced breath-sample determinations, especially for polar compounds, which tend to remain trapped in breath droplets.

Needle-Trap Device Containing a Filter: A Novel Device for Aerosol Studies.

Particles in an aerosol sample contain a portion of the total available analytes. Therefore, particle trapping is required to fully characterize a gaseous sample. Needle-trap devices (NTDs) are highly useful to this end, as they allow sampling and preconcentration of free analytes, as well as the trapping of particles. Packing sorbents into the needle creates a filter that traps solid particles or liquid droplets. However, the particle-trapping efficiency of sorbent-packed NTDs is limited, especially for nanoparticles. To address this issue, an aerogel based on electrospun polyacrylonitrile (PAN) was prepared for trapping small particles to analyze particle-bound analytes. The PAN aerogel filter was fabricated by cutting electrospun PAN fibers and removing the remaining solvent via freeze-drying to obtain a light porous fibrous structure. The PAN aerogel was heated (H-PAN) prior to packing to ensure stability during thermal desorption. The trapping efficiency of the H-PAN-packed NTD was measured using a range of conditions, with high filtration efficiencies (>99%) being obtained in all cases. The mechanical stability of the H-PAN aerogel was tested using multiple extraction/desorption cycles with and without solid sorbent particles, with results indicating high repeatability (n = 94, relative standard deviation (RSD) <6%). The developed NTD was compared to thin-film microextraction with respect to their ability to characterize breath samples obtained with or without face masks; the NTD was able to trap both free and droplet-bound analytes, while thin-film microextraction was only able to extract free analytes, which is fully reflected in concentrations obtained with these two methods.

Determination of free concentration of endocannabinoids in brain tissue.

The release of metabolites from their bound to free forms is the main regulatory path in living species. Therefore, the ability to determine the free concentrations of small molecules is highly critical in many biological samples. The main challenges in achieving this task are the interferences inherent to complex matrices and the ability to distinguish between the free and total concentrations. This paper presents a non-invasive microextraction method that enables the determination of endocannabinoids in brain tissue. The proposed method is based on two key principles: the availability of the free concentration of endocannabinoids for partitioning to the solid-phase microextraction (SPME) fiber; and negligible depletion enabled by the small volume of extraction phase on the fiber. These features allow the presented SPME method to provide information about the free concentration of analytes without disturbing the binding equilibrium between the analytes and the matrix. The determination of spiked samples with known concentrations enables the percentage of analyte bound to the tissue to be calculated, which can then be applied to calculate the total concentration from the determined free concentration. This manuscript focuses on the determination of the free concentration and tissue binding percentages of endocannabinoids in brain tissue. Significantly, SPME's small size and potential for non-invasive sampling enable its application in live animal subjects with minimal tissue damage.

Free versus droplet-bound aroma compounds in sparkling beverages.

The initial experience of a beverage's flavor after opening the bottle is created by a combination of the gas phase and droplet-bound odorants. However, most studies do not consider this combination, and focus on the odor-active components in the liquid or gas phase, separately. To cover this aspect, a filter from pyrolyzed polyacrylonitrile fiber was packed inside thermal desorption unit liner and used for trapping droplet-bound odorants. Additionally, polydimethylsiloxane coated thin-film was applied for extraction of gas-phase aroma. Following trapping/extraction, the devices were desorbed and compounds were separated using GC-MS. The odorants in commercial sparkling beverages were quantified immediately after opening the bottle to mimic real-life conditions of the consumer's experience of the flavor. The reported results provide a more comprehensive understanding of flavor perception in effervescent drinks by considering both gas and droplet phase.

Simultaneous determination of exhaled breath vapor and exhaled breath aerosol using filter-incorporated needle-trap devices: A comparison of gas-phase and droplet-bound components.

Breath-composition analysis is a well-established, non-invasive method for early disease diagnosis and investigating exposure history. However, this analytical approach is hampered by the aerosol nature of breath samples and/or low concentrations of volatile organic compounds. Conventionally, two separate methods have been applied to study gas phase and breath droplets, although these approaches are expensive and time-consuming. To address this issue, for the first time a needle-trap device packed with Carboxen, which served as a sorbent for the extraction of volatile analytes from the gas-phase, and electrospun polyacrylonitrile filter, which used to capture breath aerosol was applied to breath characterization. The performance of the developed device was subsequently compared to that of Carboxen-loaded thin-film microextraction, which was employed for the first time to extract free gas-phase components. Both methods were optimized, validated, and applied for the screening of breath samples obtained from volunteers. Obtained figures of merits are as follows: limits of detection (0.01-0.2 ng mL-1), recovery (81-108%) and repeatability (<13%). To investigate the effect of droplets, breath samples acquired with and without a face mask were compared. While both methods yielded similar results for the breath samples obtained with the mask, the needle-trap device was able to provide higher concentrations of volatile organic compounds for the samples acquired without a mask due to its enhanced ability to trap droplets. Additionally, tests were also conducted to investigate breath composition after accidental exposure to chemicals. The results of these tests revealed that polar compounds tended to partition to breath droplets and were eliminated from the body more quickly, while non-polar compounds tended to remain in the gas phase and were eliminated at a slower rate.

Determination of Droplet-Bound and Free Gas-Phase Fragrances Using a Filter-Incorporated Needle-Trap Device and Solid-Phase Microextraction Technologies.

Some of the fragrance compounds in aerosols tend to remain trapped inside the droplets. The ability to capture these droplets would make it possible to desorb and transfer the analytes dissolved within for determination. In this study, we design a novel filter-incorporated needle-trap device and use it to capture fragrance compounds in droplets as well as the gas phase of seven aerosol spray samples. For comparison, thin-film and solid-phase microextraction were also employed to extract gas-phase-borne fragrances from the same sprays. The results revealed that the filter-incorporated needle-trap device enables the extraction of total concentrations due to its ability to trap fragrance-containing droplets, whereas thin-film and solid-phase microextraction are only able to extract unbound compounds present in the gas phase. In addition, the developed needle-trap device provided acceptable results, proving its applicability for the analysis of aroma in other samples, such as beer and soda.

Preparation of amine-modified lignin and its applicability toward online micro-solid phase extraction of valsartan and losartan in urine samples.

In the present work, with the focus on an environmentally-friendly approach, some gels were prepared by synthesizing amine-modified lignin, extracted from sugarcane bagasse, and further esterification and subsequent freeze-drying. These lignin-based gels were implemented as extractive phases in an online micro-solid phase extraction (µSPE) setup in conjunction with high performance liquid chromatography (HPLC) with UV detector. The developed method was used for analytical determination of valsartan and losartan in urine samples. To study the effect of the functionalization process, the efficiency of the unmodified lignin and the functionalized lignin were compared both in the absence and the presence of graphene oxide (GO), presumably as a suitable doping agent. Surprisingly, higher extraction efficiency for the functionalized lignin, compared to both unmodified lignin and GO was observed. The amination process for the prepared gel was analyzed and proved by CHNS elemental analysis and Fourier transform infrared (FT-IR) spectroscopy. The morphology of sorbet was investigated via scanning electron microscope (SEM) imaging and a nanoscale cauliflower feature was observed. The method was optimized and subsequently applied to the analysis of the urine samples. Limits of detection (LOD) of 8 and 6 µg L - 1, limits of quantification (LOQ) of 27 and 20 µg L - 1 and linear dynamic range (LDR) of 27-2000 and 20-2000 µg L - 1 with intraday relative standard deviations (RSD%) of 4 and 3% were obtained for valsartan and losartan, respectively. The whole online µSPE-HPLC setup was conveniently used for the analysis of a patient urine sample and a quantity of 352 µg L - 1 of losartan was found. Acceptable relative recoveries (109-108 and 95-94% for valsartan and losartan) revealed the analytical potential of the method for the determination of drugs in complex urine samples.

Generic extraction medium: From highly polar to non-polar simultaneous determination.

Sample preparation for non-target analysis is challenging due to the difficulty in the extraction of polar and non-polar analytes simultaneously. Most commercial solid sorbents lack the proper comprehensiveness for extraction of analytes with different physiochemical properties. A possible key is the combination of hydrophobic polymer and hydrophilic surface functional groups in solid based extraction methods in order to generate the susceptibility for retaining both polar and non-polar analytes. To pursue this goal, in this study, four polar groups including NH2, NO2, COOH, and COCH3 were chemically bound to Amberlite XAD-4 substrate in order to prepare a generic extraction platform. To validate the applicability of extractive phases, 22 analytes possessing wide range of polarities (LogP range between -2 and +7) were chosen for extraction using the synthesized polymers by online micro solid phase extraction (µ-SPE) and further analyzed with high-performance liquid chromatography and UV-Vis detection (HPLC-UV). The recovery data were compared with commercial sorbents by t-test, principal component analysis (PCA) and hierarchical cluster analysis (HCA). Amberlite XAD-4 modified with COOH group (XAD-COOH) revealed extraction efficiencies statistically better than commercially available sorbents including LiChrolut® EN, Oasis® HLB and Amberlite® XAD-4®. The reproducibility and repeatability of XAD-COOH were also studied and acceptable results were obtained. Furthermore, the swellability of polymers was also measured and the results were comparable with commercial ones. To evaluate the extraction ability of XAD-COOH in real sample matrix, water sample near a heavy crude oil spill, urine and hospital wastewater were analyzed. Comparison of the data with LiChrolut® EN corroborates the dominance of XAD-COOH for screening analysis.

Amine modified magnetic polystyrene for extraction of drugs from urine samples.

Polystyrene is one of the best candidates as the extracting medium due to its high stability in different media and acceptable extraction capability. However, the hydrophobic nature and low wettability of polystyrene limits its application to non-polar analytes. To resolve this limitation, in this project, amine groups were chemically attached to the surface of magnetic polystyrene. The resulting hydrophilic magnetic particles were expected to be capable of extracting both polar and non-polar analytes. Non-steroidal anti-inflammatory drugs (NSAIDs) were chosen for testing the applicability of modified magnetic polystyrene according to the importance of their analysis and also their wide polarity range. Major parameters associated with the extraction procedure were optimized using central composite design (CCD) method and pH 3, extraction time of 15 min, desorption volume of 350 µL and desorption time of 4 min were chosen as optimized values. Under these conditions, figures of merit were calculated including: linear dynamic range (0.5-1000 µg L-1), linear equation and limits of detection (0.1-3 µg L-1). To investigate the method precision, inter-day, intra-day and synthesis-to-synthesis relative standard deviation (RSD) were studied (<12%). All studies were conducted using blank urine samples spiked with aspirin, salicylic acid, ibuprofen, diclofenac and mefenamic acid. Naproxen was chosen as the internal standard and high-performance liquid chromatography-UV-Vis (HPLC-UV) was employed for the subsequent determination after extraction. To evaluate the applicability of the method for real sample analysis, urine samples from patients under treatment were analyzed and acceptable results were obtained. The aminated magnetic polystyrene revealed superior extraction efficiency, much higher than polystyrene before functionalization. In addition, hospital wastewater sample was tested and acceptable extraction efficiencies were obtained.

A single-step synthesized supehydrophobic melamine formaldehyde foam for trace determination of volatile organic pollutants.

Superhydrophobic materials have attracted many attentions in recent years while their application in sample preparation remained almost intact. In this project, a rough surface of melamine formaldehyde foam was silanized by chemical deposition of trichloromethylsilane to form a highly porous and superhydrophobic material, presumably a suitable medium for extracting non-polar compounds such as benzene and its methyl derivatives. The prepared sorbent was packed in a needle for the headspace needle-trap microextraction of benzene, toluene, ethylbenzene and xylenes (BTEX). Major parameters associated with the extraction/desorption processes were considered for optimization. Under the optimized condition, the linear dynamic range was from 20 to 1000ngL-1 (R2>0.98). For evaluating the method precision, inter-day, intra-day and needle-to-needle relative standard deviations (RSD%) were calculated (<13%) for water samples spiked at 500ngL-1 of BTEX. The LOD values were in the range of 5-10ngL-1 using gas chromatography-flame ionization detector (GC-FID). Finally, hookah water was considered as suspicious real sample, assumed to contain volatile organic pollutants. Among these pollutants, toluene was identified, at the concentration level of 439ngL-1, in one of the hookah samples while benzene was detectable at much lower level. Also, some other organic pollutants were identified in the smoke and hookah water using GC-mass spectrometry (GC-MS). In addition, the suspicious BTEX-containing samples from petrochemical waste water of Asalooye (Persian Gulf) were analyzed.