Rapid Analysis of Fentanyl and Fentanyl Analogues from Whole Blood Using SPME Coupled to the Microfluidic Open Interface.

Fentanyl and its analogues are potent opioids that pose a significant threat to society. Over the last several years, considerable focus has been on the concerning trend of increasing fentanyl usage among drug users. Fentanyl analogues are mainly synthesized to evade analytical detection or increase their potency; thus, very low concentrations are sufficient to achieve a therapeutic effect. In an effort to help combat the synthetic opioid epidemic, developing targeted mass spectrometric methods for quantifying fentanyl and its analogues at ultralow concentrations is incredibly important. Most methods used to analyze fentanyl and its analogues from whole blood require manual sample preparation protocols (solid-phase extraction or liquid-liquid extraction), followed by chromatographic separation and mass spectrometric detection. The main disadvantages of these methods are the tedious sample preparation workflows, resulting in lengthy analysis times. To mitigate these issues, we present a targeted method capable of analyzing 96 samples containing fentanyl, several fentanyl analogues, and a common fentanyl (analogue) precursor simultaneously in 2.4 min per sample. This is possible by using a high-throughput solid phase microextraction workflow on the Concept96 autosampler followed by manual coupling of solid-phase microextraction fibers to the microfluidic open interface for tandem mass spectrometry analysis. Our quantitative method is capable of extremely sensitive analysis, with limits of quantification ranging from 0.002 to 0.031 ng mL-1 and linearity ranging from 0.010 to 25.0 ng mL-1. The method shows very good reproducibility (1-18%), accuracy (81-100%) of calibration and validation points, and good interday reproducibility (6-15%).

Proteomic Analysis of Human Saliva via Solid-Phase Microextraction Coupled with Liquid Chromatography-Mass Spectrometry.

Proteomics of human saliva samples was achieved for the first time via biocompatible solid-phase microextraction (bio-SPME) devices. Upon introduction of a porogen to a conventional C18 coating, porous C18/polyacrylonitrile (PAN) SPME blades were able to extract peptides up to 3.0 kDa and more peptides than commercial SPME blades. Following Trypsin digestion, salivary proteomic analysis was achieved via SPME-LC-MS/MS. Seven endogenous proteins were consistently identified in all saliva samples via bio-SPME. Taking advantage of this strategy, untargeted peptidomics was applied for the comparison of saliva samples between healthy and SARS-CoV-2 positive individuals. The results showed clear peptidomic differences between the viral and healthy saliva samples. This proof-of-concept study demonstrates the potential of bio-SPME-LC-MS/MS for peptidomics and proteomics in biomedical applications.

Coupling Miniaturized Stir Bar Sorptive Dispersive Microextraction to Needle-Based Electrospray Ionization Emitters for Mass Spectrometry: Determination of Tetrahydrocannabinol in Human Saliva as a Proof of Concept.

Direct coupling of sample preparation with mass spectrometry (MS) can speed up analysis, enabling faster decision-making. In such combinations, where the analysis time is mainly defined by the extraction procedure, magnetic dispersive solid-phase extraction emerges as a relevant technique because of its rapid workflow. The dispersion and retrieval of the magnetic sorbent are typically uncoupled stages, thus reducing the potential simplicity. Stir bar sorptive dispersive microextraction (SBSDME) is a novel technique that integrates both stages into a single device. Its miniaturization (mSBSDME) makes it more portable and compatible with low-availability samples. This article reports the direct combination of mSBSDME and MS using a needle-based electrospray ionization (NESI) emitter as the interface. This combination is applied to determine tetrahydrocannabinol in saliva samples, a relevant societal problem if the global consumption rates of cannabis are considered. The coupling requires only the transference of the magnet (containing the sorbent and the isolated analyte) from the mSBSDME to the hub of a hypodermic needle, where the online elution occurs. The application of 5 kV on the needle forms an electrospray on its tip, transferring the ionized analyte to the MS inlet. The excellent performance of mSBSDME-NESI-MS/MS relies on the sensitivity (limits of detection as low as 2.25 ng mL-1), the precision (relative standard deviation lower than 15%), and the accuracy (relative recoveries ranged from 87 to 127%) obtained. According to the results, the mSBSDME-NESI-MS/MS technique promises faster and more efficient chemical analysis in MS-based applications.

Preparation of Monolith for Online Extraction and LC-MS Analysis of ß-Estradiol in Serum Via a Simple Multicomponent Reaction.

Multicomponent reactions offer efficient and environmentally friendly strategies for preparing monoliths suitable for applications in analytical chemistry. In the described study, a multicomponent reaction was utilized for the one-pot miniaturized preparation of a poly(propargyl amine) polymer inside commercial silica-lined PEEK tubing. The reaction involved only small amounts of reagents and was characterized by atom economy. The resulting monolithic column was incorporated into an autosampler system for the online extraction and cleanup of ß-estradiol from human serum. Sample pretreatment was simplified to a simple dilution with methanol and centrifugation to remove proteins. The resulting platform included LC-MS analysis in multiple reaction monitoring for quantitative analysis of ß-estradiol. The method was validated in serum, demonstrating practical applicability for the monitoring of fertile women. Recoveries were above 94%, and LOD and LOQ values at 0.008 and 0.18 ng mL-1, respectively. The developed platform proved to be competitive with previous methods for solid-phase microextraction of ß-estradiol in serum, with comparable recovery and sensitivity but with the advantage of nearly complete automation. The environmental impact of the process was evaluated as acceptable due to the miniaturization of the monolith synthesis and the automation of extraction. The drawback associated with the LC-MS technique can be reduced by the inclusion of additional analytes in a single investigation. The work demonstrates that multicomponent reactions are versatile, economical, and possibly a green methodology for producing reversed-phase and mixed-mode sorbents, enabling miniaturization of the entire analytical procedure from the preparation of extraction sorbents to analysis.

Identifying potential breath biomarkers for early diagnosis of papillary thyroid cancer based on solid-phase microextraction gas chromatography-high resolution mass spectrometry with metabolomics.

INTRODUCTION: Thyroid cancer incidence rate has increased substantially worldwide in recent years. Fine needle aspiration biopsy (FNAB) is currently the golden standard of thyroid cancer diagnosis, which however, is invasive and costly. In contrast, breath analysis is a non-invasive, safe and simple sampling method combined with a promising metabolomics approach, which is suitable for early cancer diagnosis in high volume population. OBJECTIVES: This study aims to achieve a more comprehensive and definitive exhaled breath metabolism profile in papillary thyroid cancer patients (PTCs). METHODS: We studied both end-tidal and mixed expiratory breath, solid-phase microextraction gas chromatography coupled with high resolution mass spectrometry (SPME-GC-HRMS) was used to analyze the breath samples. Multivariate combined univariate analysis was applied to identify potential breath biomarkers. RESULTS: The biomarkers identified in end-tidal and mixed expiratory breath mainly included alkanes, olefins, enols, enones, esters, aromatic compounds, and fluorine and chlorine containing organic compounds. The area under the curve (AUC) values of combined biomarkers were 0.974 (sensitivity: 96.1%, specificity: 90.2%) and 0.909 (sensitivity: 98.0%, specificity: 74.5%), respectively, for the end-tidal and mixed expiratory breath, indicating of reliability of the sampling and analysis method CONCLUSION: This work not only successfully established a standard metabolomic approach for early diagnosis of PTC, but also revealed the necessity of using both the two breath types for comprehensive analysis of the biomarkers.

Volatile fingerprints of beef cooking methods using sol-gel-based solid-phase microextraction (SPME) and direct analysis in real-time mass spectrometry (DART-MS).

RATIONALE: The aroma profile of food is a complex mixture of volatile compounds that constitutes a major component of the overall eating experience. The food service industry and chefs therefore constantly seek ways to investigate and thereby enhance the aroma profile. Oven cooking, sous vide and pan fry are three cooking methods of beef commonly practised by chefs. Near real-time analysis of volatile compounds from these three cooking methods will provide insight into respective volatile fingerprints and help improve cooking techniques. METHODS: Volatile compounds from three beef cooking methods were captured using an in-house sol-gel based solid phase microextraction (SPME) method and analysed using direct analysis in real-time mass spectrometry (DART-MS). A volatile organic compound (VOC) standard was used to demonstrate successful implementation of the sol-gel coating technique. Volatile features discriminating the three cooking methods were shortlisted and statistically assessed by univariate and multivariate analyses. RESULTS: The VOC standard was successfully adsorbed by the sol-gel method and detected by DART-MS. Hierarchical cluster analysis clearly demarcated three beef cooking methods based on their volatile fingerprints. Out of 65 significant features differentiating the cooking methods, 50 were at highest concentrations from pan-fry cooking only, followed by 14 with highest concentrations from oven cooking followed by pan frying. Sous vide followed by pan frying showed lowest concentrations of almost all volatile features. CONCLUSIONS: The sol-gel-based solid-phase microextraction technique combined with DART-MS was successful in differentiating beef cooking methods based on their volatile fingerprints. A workflow for rapid assessment of the volatile profile from beef cooking methods was established, providing a baseline to further explore volatile profiles from other key ingredients.

Discrimination and characterization of volatile organic compounds in Lonicerae Japonicae flos and Lonicerae flos using multivariate statistics combined with headspace gas chromatography-ion mobility spectrometry and headspace solid-phase microextraction gas chromatography-mass spectrometry techniques.

RATIONALE: The volatile organic compounds (VOCs) of Lonicerae Japonicae flos (LJF) and Lonicera flos (LF) play a pivotal role in determining their sensory characteristics, medicinal properties, and subsequent impact on market pricing and consumer preferences. However, the differences and specificity of these VOCs remain obscure. Hence, it is crucial to conduct a comprehensive characterization of the VOCs in LJF and LF and pinpoint their potential differential VOCs. METHODS: In this study, headspace gas chromatography-ion mobility spectrometry (HS-GC/IMS) and headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC/MS) were employed to comprehensively investigate the compositional characteristics and distinctions in VOCs between LJF and LF. Multivariate statistical analysis was used to identify candidate differential VOCs of LJF and LF samples. RESULTS: A total of 54 and 88 VOCs were identified using HS-GC/IMS and HS-SPME-GC/MS analysis, respectively. Primary VOCs detected in LJF include leaf alcohol, (E)-2-hexen-1-ol dimer, 2-octyn-1-ol, and (E)-3-hexen-1-ol. Key VOCs prevalent in LF encompass farnesol, heptanoic acid, octanoic acid, and valeric acid. Multivariate statistical analysis indicates that compounds such as phenethyl alcohol and leaf alcohol were selected as potential VOCs for distinguishing between LJF and LF. CONCLUSION: This research conducted a comprehensive analysis of the fundamental volatile components in both LJF and LF. It subsequently elucidated the distinctions and specificities within their respective VOC profiles. And this study enables differentiation between LJF and LF through the analysis of VOCs, offering valuable insights for enhancing the quality control of both LJF and LF.

Embedding Mixed Sorbents in Binder: Solid-Phase Microextraction Coating with Wide Extraction Coverage and Its Application in Environmental Water Analysis.

Solid-phase microextraction (SPME) is a simple and highly effective sample-preparation technique for water analysis. However, the extraction coverage of a given SPME device with a specific coating can be an issue when analyzing multiple environmental contaminants. Therefore, instead of synthesizing one sorbent material with dual or multiple functions, we investigated a new strategy of preparing SPME blades using a homogeneous slurry made by mixing three different sorbent particles─namely, hydrophobic/lipophilic balanced (HLB), HLB-weak cationic exchange (HLB-WCX), and HLB-weak anionic exchange (HLB-WAX)─with a polyacrylonitrile (PAN) binder. The developed coating is matrix compatible, as the binder functions not only as a glue for immobilizing the sorbent particles but also as a porous filter, which only allows small molecules to enter the pores and interact with the particles, thus avoiding contamination from large elements. The results confirmed that the proposed mixed-coating SPME device provides good extraction performance for polar and nonpolar as well as positively and negatively charged compounds. Based on this device, three comprehensive analytical methodologies─high-throughput SPME-LC-MS/MS (for the quantitative analysis of targeted drugs of abuse and artificial sweeteners), in-bottle SPME-LC-high resolution MS (HRMS) (for the untargeted screening of organic contaminants), and on-site drone sampling SPME-LC-HRMS (for on-site sampling and untargeted screening)─were developed for use in environmental water analysis. The resultant data confirm that the proposed strategies enable comprehensive water quality assessment by using a single SPME device.

Solid-phase microextraction coupled to comprehensive multidimensional gas chromatography for food analysis.

Solid-phase microextraction and comprehensive multidimensional gas chromatography represent two milestone innovations that occurred in the field of separation science in the 1990s. They have a common root in their introduction and have found a perfect coupling in their evolution and applications. This review will focus on food analysis, where the paradigm has changed significantly over time, moving from a targeted analysis, focusing on a limited number of analytes at the time, to a more holistic approach for assessing quality in a larger sense. Indeed, not only some major markers or contaminants are considered, but a large variety of compounds and their possible interaction, giving rise to the field of foodomics. In order to obtain such detailed information and to answer more sophisticated questions related to food quality and authenticity, the use of SPME-GC × GC-MS has become essential for the comprehensive analysis of volatile and semi-volatile analytes. This article provides a critical review of the various applications of SPME-GC × GC in food analysis, emphasizing the crucial role this coupling plays in this field. Additionally, this review dwells on the importance of appropriate data treatment to fully harness the results obtained to draw accurate and meaningful conclusions.

The influence of drying and storage conditions on the volatilome and cannabinoid content of Cannabis sativa L. inflorescences.

The increasing interest in hemp and cannabis poses new questions about the influence of drying and storage conditions on the overall aroma and cannabinoids profile of these products. Cannabis inflorescences are subjected to drying shortly after harvest and then to storage in different containers. These steps may cause a process of rapid deterioration with consequent changes in precious secondary metabolite content, negatively impacting on the product quality and potency. In this context, in this work, the investigation of the effects of freeze vs tray drying and three storage conditions on the preservation of cannabis compounds has been performed. A multi-trait approach, combining both solid-phase microextraction (SPME) two-dimensional gas chromatography coupled to mass spectrometry (SPME-GC × GC-MS) and high-performance liquid chromatography (HPLC), is presented for the first time. This approach has permitted to obtain the detailed characterisation of the whole cannabis matrix in terms of volatile compounds and cannabinoids. Moreover, multivariate statistical analyses were performed on the obtained data, helping to show that freeze drying conditions is useful to preserve cannabinoid content, preventing decarboxylation of acid cannabinoids, but leads to a loss of volatile compounds which are responsible for the cannabis aroma. Furthermore, among storage conditions, storage in glass bottle seems more beneficial for the retention of the initial VOC profile compared to open to air dry tray and closed high-density polyethylene box. However, the glass bottle storage condition causes formation of neutral cannabinoids at the expenses of the highly priced acid forms. This work will contribute to help define optimal storage conditions useful to produce highly valuable and high-quality products.

Comprehensive characterization of organics in oil sands process water in constructed mesocosms utilizing multiple analytical methods.

This study aims to provide a thorough characterization of dissolved organics in oil sands process water (OSPW) in field-based aquatic mesocosms at both molecular and bulk measurement levels using multiple analytical methods. In a 3-year outdoor mesocosm experiment, the analysis of naphthenic acid (NA) species was conducted using ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOFMS). The results revealed the removal of both total NAs (38% and 35%) and classical NAs (O2-NAs, 58% and 49%) in undiluted and half-diluted OSPW, respectively. The increased ratios of oxidized NAs (O3-O6 NAs) to classical NAs suggested a transformation trend. The results also indicated that O2-NAs with higher carbon number and lower double bond equivalent (DBE) were more easily degraded in the mesocosm systems. Biomimetic extraction using solid-phase microextraction (BE-SPME) measurement displayed 26% (undiluted OSPW) and 30% (half-diluted OSPW) decrease in total bioavailable organics over 3 years. Naphthenic acids fraction compounds (NAFCs) obtained by liquid-liquid extraction (LLE) were also determined using Fourier transform infrared spectroscopy (FTIR). Reduction in acute toxicity for undiluted (43%) and half-diluted (26%) OSPW was observed over 3 years, which are well correlated with the decreases of NAs and BE-SPME concentrations. Moreover, BE-SPME values were found to be linearly correlated with total NAs concentrations (r = 0.96) and NAFCs (r = 0.96). Additionally, the linear relationships of individual O2-O6 NA species and BE-SPME concentrations unveiled the changes in the relative abundances of O2-O6 NA species in total bioavailable organics over time in the mesocosms. The present study has provided comprehensive insights by integrating various analytical methods, contributing valuable information for assessing the effectiveness of aquatic mesocosm systems in studying the temporal changes of organics in OSPW.

Analysis of 14 ß-agonists in pork using an automated wooden tip-based solid-phase microextraction device and ultra-high-performance liquid chromatography-tandem mass spectrometry.

This study introduces a cost-effective, automated ultra-high-performance liquid chromatography-tandem mass spectrometry method for the detection of 14 ß-agonists in pork using a novel solid-phase microextraction probe composed of polyacrylonitrile and molecularly imprinted polymer. Integrated into an automated extraction device, the probe optimizes extraction prior to analysis while reducing expenses and time compared to traditional solid-phase extraction procedures. The method validation followed the Chinese National Standard (GB/T 27404-2008) and examined limits of detection, limits of quantification, matrix effects, linearity, intraday, and interday precision. Average recovery rates ranged from 71.6% to 82.2%, with relative standard deviations less than 15%. Limits of detection and limits of quantification ranged from 0.09 to 0.39 and 0.27 to 0.99 µg/kg, respectively. The new method identified positive samples more accurately than the current National Standard GB/T 31658.22-2022 and demonstrated its potential for routine assessment and regulatory compliance in the detection of ß-agonists in pork.

Alien species water hyacinth realizes waste into treasure: The preparation of biomass sorbent to determine benzoylurea insecticides in tea products.

A fast and effective analytical method with biomass solid-phase microextraction sorbent combined with a high-performance liquid chromatography-ultraviolet detector was proposed for the determination of benzoylurea (BU) insecticides in tea products. The novel sorbent was prepared by activating and then carbonizing water hyacinth with a fast growth rate and low application value as raw material and showed a high specific surface area and multiple interactions with analytes, such as electrostatic action, hydrogen bonding, and π-π conjugation. After optimizing the three most important extraction parameters (pH [X1], sample loading rate [X2], and solution volume [X3]) by Box-Behnken design, the as-established analytical method showed good extraction performance: excellent recovery (80.13%-106.66%) and wide linear range (1-400 µg/L) with a determination coefficient of 0.9992-0.9999, a low limit of detection of 0.02-0.1 µg/L and the satisfactory practical application results in tea products. All these indicate that the water hyacinth-derived material has the potential as a solid-phase extraction sorbent for the detection and removal of BU insecticides from tea products, and at the same time, it can also achieve the effect of rational use of biological resources, maintaining ecological balance, turning waste into treasure, and achieving industrial production.

Rearing and 60Co radiation do not affect attractiveness but alter the volatile profiles released by Anastrepha obliqua calling males.

Calling males of Anastrepha obliqua release volatile compounds to attract conspecific males to form leks and females to mate. Male volatiles from Mexican and Brazilian populations of A. obliqua have been previously identified. However, there are differences in the number and identity of volatile compounds between the populations. These differences in volatile profiles may be due to male origin (e.g. wild or mass-reared flies) or methodological issues (e.g. sampling techniques). In this study, we evaluated the attractiveness of wild, laboratory non-irradiated, and laboratory-irradiated flies under semi-field conditions. Male volatiles were collected using dynamic headspace sampling (DHS) and solid-phase microextraction (SPME) techniques, and identified using gas chromatography-coupled mass spectrometry. The results showed no difference in the attractiveness of wild, laboratory non-irradiated, and irradiated males to females. However, the number of captured females differed according to the origin; wild and non-irradiated females were captured more frequently than the irradiated flies. A total of 21 compounds were found using SPME, whereas only 12 were collected using DHS, although the relative amounts of these compounds were higher than those obtained using the former sampling technique. In addition, only laboratory non-irradiated males released α-pinene and menthol, which have not been previously reported in this fruit fly species. Additionally, we identified novel compounds in A. obliqua; however, certain compounds previously reported were not detected. This study suggests that despite the qualitative and quantitative variations in the volatile profiles of A. obliqua males, their attractiveness was unaffected.

Integrative metagenomics, volatilomics and chemometrics for deciphering the microbial structure and core metabolic network during Chinese rice wine (Huangjiu) fermentation in different regions.

Huangjiu is a spontaneously fermented alcoholic beverage, that undergoes intricate microbial compositional changes. This study aimed to unravel the flavor and quality formation mechanisms based on the microbial metabolism of Huangjiu. Here, metagenome techniques, chemometrics analysis, and headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS) metabolomics combined with microbial metabolic network were employed to investigate the distinctions and relationship between the microbial profiles and the quality characteristics, flavor metabolites, functional metabolic patterns of Huangjiu across three regions. Significant variations (P < 0.05) were observed in metabolic rate of physicochemical parameters and biogenic amine concentration among three regions. 8 aroma compounds (phenethyl acetate, phenylethyl alcohol, isobutyl alcohol, ethyl octanoate, ethyl acetate, ethyl hexanoate, isoamyl alcohol, and diethyl succinate) out of 448 volatile compounds were identified as the regional chemical markers. 25 dominant microbial genera were observed through metagenomic analysis, and 13 species were confirmed as microbial markers in three regions. A metabolic network analysis revealed that Saccharomycetales (Saccharomyces), Lactobacillales (Lactobacillus, Weissella, and Leuconostoc), and Eurotiales (Aspergillus) were the predominant populations responsible for substrate, flavor (mainly esters and phenylethyl alcohol) metabolism, Lactobacillales and Enterobacterales were closely linked with biogenic amine. These findings provide scientific evidence for regional microbial contributions to geographical characteristics of Huangjiu, and perspectives for optimizing microbial function to promote Huangjiu quality.

Microextraction techniques for occupational biological monitoring: Basic principles, current applications and future perspectives.

The application of green microextraction techniques (METs) is constantly being developed in different areas including pharmaceutical, forensic, food and environmental analysis. However, they are less used in biological monitoring of workers in occupational settings. Developing valid extraction methods and analytical techniques for the determination of occupational indicators plays a critical role in the management of workers' exposure to chemicals in workplaces. Microextraction techniques have become increasingly important because they are inexpensive, robust and environmentally friendly. This study aimed to provide a comprehensive review and interpret the applications of METs and novel sorbents and liquids in biological monitoring. Future perspectives and occupational indicators that METs have not yet been developed for are also discussed.

Volatile Organic Compounds from Offspring of Stingless Bee Sacrificed in Hygienic Behavior Test.

This study shows the profile of volatile organic compounds (VOCs) from pupae and larvae of Melipona quadrifasciata anthidioides Lepeletier subjected to three death induction techniques for hygienic behavior (HB) studies: freezing in liquid nitrogen (LN2), freezing in a freezer (FRZ) and piercing of offspring with an entomological pin (PIN). The VOCs from larvae and pupae were obtained through headspace solid-phase microextraction and characterized using gas chromatography coupled to mass spectrometry. In addition, an HB test was performed on the colonies. The main classes of VOCs were hydrocarbons, terpenes and alcohols. Multivariate analysis was applied and showed that there was a separation in the compound profiles between the different treatments. The HB test in the colonies showed that 24 hours after the application of the techniques, the bees removed more dead larvae in LN2 treatment (83.5 %), while after 48 hours more larvae were removed in the LN2 and FRZ treatments (92.3 %). When compared to pupae removal, larvae removal was significantly faster in LN2.

Micro-Morphology characterization and HS-SPME-GC-MS Analysis of Floral parts of Quararibea funebris (La Llave) Vischer, traditionally known as Rosita de Cacao.

The flowers of Quararibea funebris are used to make a traditional drink called tejate, to which they add aroma, flavor and consistency. The study aims to profile the morphoanatomy of the floral parts of Q. funebris and analyze the changes in its volatile chemical composition during the drying process from 0 to 180 days by HS-SPME-GC-MS. The calyx, corolla, androecium, and gynoecium have distinct characteristics, such as non-glandular fused stellate trichomes, calcium oxalate crystals, and large secretory ducts. Histochemical localization reveals the presence of mucilage and total lipids in all parts of the flower. The chemical analysis of the essential oil, extracted from the flowers, showed that transfarnesol and geraniol were the most abundant compounds, with a yield of 0.04 %. HS-SPME analysis indicated that fresh flowers had a more complex composition than dried ones. In total, 31 components were identified. Nonanal and geranyl acetone were found to be distinctive components of dried flowers. Microscopic examination helps in identifying and authenticating raw materials and also reveals the presence of secretory ducts in all floral parts, which is a distinctive feature. The chemical profile of volatiles provides an important parameter for the evaluation of the quality of Rosita de Cacao raw materials.

Exploring the Chemical Constituents and Nutritive Potential of Bee Drone (Apilarnil): Emphasis on Antioxidant Properties.

A lesser-known bee product called drone brood homogenate (DBH, apilarnil) has recently attracted scientific interest for its chemical and biological properties. It contains pharmacologically active compounds that may have neuroprotective, antioxidant, fertility-enhancing, and antiviral effects. Unlike other bee products, the chemical composition of bee drone larva is poorly studied. This study analyzed the chemical compostion of apilarnil using several methods. These included liquid chromatography-mass spectrometry (LC-MS/MS) and a combination of gas chromatography/mass spectrometry with solid phase micro-extraction (SPME/GC-MS). Additionally, antioxidant activity of the apilarnil was assessed using 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. A chemical assessment of apilarnil showed that it has 6.3±0.00, 74.67±0.10 %, 3.65±0.32 %, 8.80±1.01 %, 13.16±0.94 %, and 8.79±0.49 % of pH, moisture, total lipids, proteins, flavonoids, and carbohydrates, respectively. LC-MS/MS analysis and molecular networking (GNPS) of apilarnil exhibited 44 compounds, including fatty acids, flavonoids, glycerophospholipids, alcohols, sugars, amino acids, and steroids. GC-MS detected 30 volatile compounds in apilarnil, mainly esters (24 %), ketones (23.84 %), ethers (15.05 %), alcohols (11.41 %), fatty acids (10.06), aldehydes (6.73 %), amines (5.46), and alkene (5.53 %). The antioxidant activity of apilarnil was measured using DPPH with an IC50 of 179.93±2.46 µg/ml.

In situ fabrication of covalent organic frameworks on solid-phase microextraction probes coupled with electrospray ionization mass spectrometry for enrichment and determination of androgens in biosamples.

Solid-phase microextraction (SPME) coupled with electrospray ionization mass spectrometry (ESI-MS) was developed for rapid and sensitive determination of endogenous androgens. The SPME probe is coated with covalent organic frameworks (COFs) synthesized by reacting 1,3,5-tri(4-aminophenyl)benzene (TPB) with 2,5-dioctyloxybenzaldehyde (C8PDA). This COFs-SPME probe offers several advantages, including enhanced extraction efficiency and stability. The analytical method exhibited wide linearity (0.1-100.0 µg L-1), low limits of detection (0.03-0.07 µg L-1), high enrichment factors (37-154), and satisfactory relative standard deviations (RSDs) for both within one probe (4.0-14.8%) and between different probes (3.4-12.7%). These remarkable performance characteristics highlight the reliability and precision of the COFs-SPME-ESI-MS method. The developed method was successfully applied to detect five kinds of endogenous androgens in female serum samples, indicating that the developed analytical method has great potential for application in preliminary clinical diagnosis.