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Despite the importance of monitoring and correlating neurotransmitter concentrations in the brain with observable behavior and brain areas in which they act, in vivo measurement of multiple neurochemicals in the brain remains a challenge. Here, we propose an alternative solid phase microextraction-based (SPME) chemical biopsy approach as a viable method for acquirement of quantitative information on multiple neurotransmitters by one device within a single sampling event, with multisite measurement capabilities and minimized invasiveness, as no tissue is removed. The miniaturized SPME probe developed for integrated in vivo sampling/sample preparation has been thoroughly optimized with respect to probe shape, desorption solvent, and extracting phase tailored for extraction of small hydrophilic molecules via synthesis and functionalization of the SPME coating. Experimental evaluations of sampling time and storage strategy led to achieving appropriate temporal resolution versus recovery balance as well as little or no analyte loss, respectively. Validation of the developed SPME-HPLC-MS/MS protocol in a surrogate brain matrix yielded satisfactory accuracies of 80–100%, precision below 17%, as well as linear dynamic range and limits of quantitation suitable for determining neurochemicals at physiologically relevant levels. Finally, we present a proof-of-concept in vivo application in macaque brain, where several target neurotransmitters were extracted simultaneously from three brain areas. The developed probe and protocol are herein presented as a potential powerful addition to the existing in vivo toolbox for measurements of local levels of neurochemicals in multiple brain systems implicated in the neuropathology of psychiatric disorders.

A novel hydrophilic−lipophilic balanced (HLB) thin film solidphase microextraction (TF-SPME) device is proposed for polarity-balanced determinations of volatile organic compounds. The proposed HLB particles used in the preparation of these membranes were prepared using a precipitation polymerization technique and determined to have a specific surface area of 335 m 2 /g with an average pore diameter of 13 Å. Membranes prepared from these particles were found to extract 1.8, 2.2, 1.9, 1.7, 2.0, and 1.3 times more benzene, 2-pentanone, 1-nitropropane, pyridine, 1-pentanol, and octane, respectively, than the established divinylbenzene/polydimethylsiloxane (DVB/PDMS)-based membranes. Furthermore, membranes prepared from these lab-made particles were shown to extract significantly (p = 0.00047) larger amounts of these analytes than membranes prepared from comparative commercial HLB particles. The intermembrane extraction efficiency between 3 membranes was determined to be reproducible at 95% confidence for 4 different coating chemistries tested, including the DVB/PDMS membranes, and those prepared with 3 different HLB compositions. Furthermore, method reliability was established by confirming that, once extracted, modified McReynolds standards were stable on the HLB/PDMS membranes stored in thermal desorption tubes on an autosampler rack for at least 120 h, for 5 of the 6 standards, but only for 24 h for pyridine at a 95% level of confidence. Finally, using a TF-SPME enabled, portable GC/MS instrument, an entirely on-site proof of concept application was performed for the determination and quantitation of chlorination byproducts in a private hot tub, successfully identifying chloroform, bromodichloromethane, dichloroacetonitrile, chlorobenzene, benzonitrile, and benzyl chloride, while further quantifying chloroform and dichloroacetonitrile at levels of 270 and 79 ppb with %RSD values of 13% and 5%, respectively.

Detection of biomarkers in exhaled breath has been gaining increasing attention as a tool for diagnosis of specific diseases. However, rapid and accurate quantification of biomarkers associated with specific diseases requires the use of analytical methods capable of fast sampling and preconcentration from breath matrix. In this regard, solid phase microextraction and needle trap technology are becoming increasingly popular in the field of breath analysis due to the unique benefits imparted by such methods, such as the integration of sampling, extraction, and preconcentration in a single step. This review discusses recent advances in breath analysis using these sample preparation techniques, providing a summary of recent developments of analytical methods based on breath volatile organic compounds analysis, including the successful identification of various biomarkers related to human diseases.

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To simplify on-site water sampling and screening, particularly in hard-to-reach or dangerous sites, a drone equipped with a hydrophilic−lipophilic balance (HLB), thin-film solid-phase microextraction (TF-SPME) sampler was developed. The dronebased sampler was shown to protect the sorbent phase from external contamination while preventing any detectable loss of components of a spiked modified McReynolds mixture on the membrane in the sampler for at least 10 min. HLB/poly-(dimethylsiloxane) (PDMS) membranes deployed in flight on the drone sampler were demonstrated to extract disinfection byproducts, including trichloromethane, dichloroacetonitrile, 1,1,1trichloro-2-propanone, 2,2,2-trichloroethanol, benzonitrile, and benzyl nitrile, from hot tub water. When analyzed on-site, in duplicate, using hand-portable instrumentation, reasonably repeatable results were achieved (%relative standard deviations (RSD's) 5−16%). Finally, drone TF-SPME sampling of an anthropogenically impacted watercourse indicated that impact from the suspected nearby landfill site was minimal, instead suggesting that internal combustion by-products from vehicles on the nearby Highway 401 played a much larger role in contaminating the watercourse. This conclusion was supported by the confirmed presence of BTEX, styrene, isopropylbenzene, propylbenzene, and 1,3,5-trimethylbenzene. In addition to immediately identifying these compounds onsite using portable gas chromatography−mass spectrometry (GC−MS), samples were taken back to the laboratory for benchtop analysis, further supporting this conclusion.

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