Solid-phase Microextraction Technique Research Articles

Plant In Vitro Cultures of Coleus scutellarioides (L.) Benth. "Electric Lime" and Possibilities of Modification in the Biosynthesis of Volatile Compounds.

Coleus scutellarioides (L.) Benth. is a globally spread species, known for its characteristic spectacularly colorful leaves of decorative value. Thanks to its rich chemical composition, the plant is used in ethnopharmacology, and it is also regarded as having high medicinal potential. The application of in vitro cultures enables the acquisition of homogeneous certified material of high quality. Additionally, excluding the effect of biotic and abiotic factors on the plants is a way to fully recognize the influence of phytohormones on the plant morphology and the biosynthetic pathways of compound production. The best way to grow C. scutellarioides "Electric Lime" under in vitro conditions is to use the basic MS medium (Murashige and Skoog medium), enriched with naphthyl-1-acetic acid at a concentration of 0.5 mg dm-3. The analysis of volatile compounds demonstrated that the content of volatile compounds in the plants cultivated under in vivo conditions was expressed at a level of 2848.59 µg g-1, whereas in the plants bred in vitro without supplementation with phytohormones, the level was 8191.47 µg g-1. The highest content was noted for copaene, α-pinene, 1-octene-3-ol, α-selinene, sabinen, γ- and δ-cadinene, 3-octanol, and β-pinene. Aroma profiling revealed a lack of boranyl acetate, 2-hexenal, and 2-hexen-1-ol in the plants cultivated under in vivo conditions. Differences were found in the volatile composition between plants bred in vivo and in vitro, with the most significant recorded for the contents of 1-octen-3-ol and 3-octanol. The addition of plant growth regulators into the basic medium under in vitro conditions affected the percentage ratio and contents of specific compounds in plant tissues. The most intense biosynthesis of volatile compounds took place in the plants cultivated on the medium enriched with NAA at 10,579.11 µg g-1, whereas the least intense was noted for plants cultivated on the medium supplemented with BA, where it was recorded at the level of 5610.02 µg g-1. So far, there has been no research published which would pertain to the profiling of volatile compounds performed using the SPME (solid-phase microextraction) technique. Moreover, the very few studies conducted on the chemical composition of these compounds do not mention the specific variety of C. scutellarioides under analysis.

Predicting the bioavailability of polycyclic aromatic hydrocarbons in rhizosphere soil using a new novel in situ solid-phase microextraction technique

In situ measurement of the bioavailability of organic pollutants in soil is crucial for understanding their environmental behavior and assessing health risks. Due to the high heterogeneity of soil, microscale determination is crucial for achieving high accuracy, but few methods are available. In this study, microsized probes coated with polydimethylsiloxane (PDMS) were used to measure the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in soil in situ. The concentrations of PAHs enriched by the PDMS-coated probes correlated well with the results of bioassays using earthworms (R2 = 0.92–0.99) and ryegrass roots (R2 = 0.92–0.99). Compared with other chemical extraction methods, such as n-butanol extraction, the proposed method has advantages such as in situ operation, microvolume analysis, and negligible interference to the soil environment. In the soil rhizosphere zone, PAHs bioavailability decreased in the following order: rhizosphere > near-rhizosphere > far-rhizosphere. The bioavailability of PAHs in soil amended with biochar was also successfully characterized by the proposed method. Thus, this study developed an in situ and microscale method to predict the bioavailability of organic pollutants in contaminated soils and provides new insight into migration and transformation processes in rhizosphere soil.

Easy and fast synthesis of MnCo-LDH yolk-shell spheres porous composites applied electrospinning nanofibers highly effective for extracting triazole fungicides

Today, the wide utilization of triazole fungicides due to environmental damage and its side effects has raised global concern. Thus, in this investigation, polyacrylonitrile/MnCo-layered double hydroxides nanofiber was synthesized and applied as an effective and novel adsorbent at thin-film solid-phase micro-extraction technique for the quick and concurrent extraction of five triazole fungicides in fruit and vegetable samples before quantitative analysis by high-performance liquid chromatography-ultraviolet. The incorporation of MnCo-layered double hydroxides with porous structure and abundant functional groups in a polymer medium improves the extraction efficiency of nanofibers owing to hydrogen bonding and π-π interactions formed between analytes and synthesized nano-adsorbent. Various important elements that affect the extraction efficiency of the intended analytes were optimized using a time-variable approach. Under the optimum conditions, the limit of detection and quantification range from 0.1 to 0.15 and 0.3–0.5 ng mL−1, respectively.

Method development for an untargeted HS-SPME-GC–MS analysis of terpenes and cannabinoids for the geographical sourcing of Marijuana

Despite growing decriminalization of Cannabis sativa (i.e., marijuana) possession throughout the United States of America, there remains to be an ongoing interest in the detection of unlawfully possessed and transported marijuana. This issue has resulted in an increasing interest regarding the generalization and specification related to the canine detection of marijuana. More specifically, canine trainers have expressed concerns on whether canines can generalize on the odor of marijuana regardless of the origin of their training materials. This research aims to differentiate multiple marijuana headspace samples from three regions in the USA based solely on the volatile organic compounds (VOCs) found in their odor profiles. In this study, a heated headspace solid phase micro-extraction (SPME) technique was optimized and implemented for the collection of both volatile terpenes and cannabinoids from marijuana. The headspace samples were analyzed using two full-scan, untargeted, optimized methods on a gas chromatograph coupled to a mass spectrometer (GC–MS), and a variety of chemometric tools were applied to the data to enable differentiation and potential classification between sample populations. Principal component analysis and sparse partial least squares discriminant analysis (sPLS-DA) employed in this study have demonstrated a disparity between marijuana varieties based on geography using the VOCs extracted from their odor profiles. With this research, it is intended to determine some fundamental differences between Cannabis of different geographical origins and set a foundation for the development and advancement of instrumental applications for other non-contact marijuana detection techniques in support of the improvement of illicit substance detection technology.

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.

Trichoderma afroharzianum TRI07 metabolites inhibit Alternaria alternata growth and induce tomato defense-related enzymes

Identifying a viable substitute for the limited array of current antifungal agents stands as a crucial objective in modern agriculture. Consequently, extensive worldwide research has been undertaken to unveil eco-friendly and effective agents capable of controlling pathogens resistant to the presently employed fungicides. This study explores the efficacy of Trichoderma isolates in combating tomato leaf spot disease, primarily caused by Alternaria alternata. The identified pathogen, A. alternata Alt3, was isolated and confirmed through the ITS region (OQ888806). Six Trichoderma isolates were assessed for their ability to inhibit Alt3 hyphal growth using dual culture, ethyl acetate extract, and volatile organic compounds (VOCs) techniques. The most promising biocontrol isolate was identified as T. afroharzianum isolate TRI07 based on three markers: ITS region (OQ820171), translation elongation factor alpha 1 gene (OR125580), and RNA polymerase II subunit gene (OR125581). The ethyl acetate extract of TRI07 isolate was subjected to GC–MS analysis, revealing spathulenol, triacetin, and aspartame as the main compounds, with percentages of 28.90, 14.03, and 12.97%, respectively. Analysis of TRI07-VOCs by solid-phase microextraction technique indicated that the most abundant compounds included ethanol, hydroperoxide, 1-methylhexyl, and 1-octen-3-one. When TRI07 interacted with Alt3, 34 compounds were identified, with major components including 1-octen-3-one, ethanol, and hexanedioic acid, bis(2-ethylhexyl) ester. In greenhouse experiment, the treatment of TRI07 48 h before inoculation with A. alternata (A3 treatment) resulted in a reduction in disease severity (16.66%) and incidence (44.44%). Furthermore, A3 treatment led to improved tomato growth performance parameters and increased chlorophyll content. After 21 days post-inoculation, A3 treatment was associated with increased production of antioxidant enzymes (CAT, POD, SOD, and PPO), while infected tomato plants exhibited elevated levels of oxidative stress markers MDA and H2O2. HPLC analysis of tomato leaf extracts from A3 treatment revealed higher levels of phenolic acids such as gallic, chlorogenic, caffeic, syringic, and coumaric acids, as well as flavonoid compounds including catechin, rutin, and vanillin. The novelty lies in bridging the gap between strain-specific attributes and practical application, enhancing the understanding of TRI07’s potential for integrated pest management. This study concludes that TRI07 isolate presents potential natural compounds with biological activity, effectively controlling tomato leaf spot disease and promoting tomato plant growth. The findings have practical implications for agriculture, suggesting a sustainable biocontrol strategy that can enhance crop resilience and contribute to integrated pest management practices.

Skin emitted volatiles analysis for noninvasive diagnosis: the current advances in sample preparation techniques for biomedical application.

Human skin emits a series of volatile compounds from the skin due to various metabolic processes, microbial activity, and several external factors. Changes in the concentration of skin volatile metabolites indicate many diseases, including diabetes, cancer, and infectious diseases. Researchers focused on skin-emitted compounds to gain insight into the pathophysiology of various diseases. In the case of skin volatolomics research, it is noteworthy that sample preparation, sampling protocol, analytical techniques, and comprehensive validation are important for the successful integration of skin metabolic profiles into regular clinical settings. Solid-phase microextraction techniques and polymer-based active sorbent traps were developed to capture the skin-emitted volatile compounds. The primary advantage of these sample preparation techniques is the ability to efficiently and targetedly capture skin metabolites, thus improving the detection of the biomarkers associated with various diseases. In further research, polydimethyl-based patches were utilized for skin research due to their biocompatibility and thermal stability properties. The microextraction sampling tools coupled with high sensitive Gas Chromatography-Mass Spectrometer provided a potential platform for skin volatolomes, thus emerging as a state-of-the-art analytical technique. Later, technological advancements, including the design of wearable sensors, have enriched skin-based research as it can integrate the information from skin-emitted volatile profiles into a portable platform. However, individual-specific hydration, temperature, and skin conditions can influence variations in skin volatile concentration. Considering the subject-specific skin depth, sampling time standardization, and suitable techniques may improve the skin sampling techniques for the potential discovery of various skin-based marker compounds associated with diseases. Here, we have summarised the current research progress, limitations, and technological advances in skin-based sample preparation techniques for disease diagnosis, monitoring, and personalized healthcare applications.

Human Health Risk Assessment of the Photocatalytic Oxidation of BTEX over TiO2/Volcanic Glass.

This study demonstrates rapid photocatalytic oxidation of a benzene, toluene, ethylbenzene, and xylene (BTEX) mixture over TiO2/volcanic glass. The assessment of the photocatalytic oxidation of BTEX was conducted under conditions simulating those found in indoor environments affected by aromatic hydrocarbon release. We show, under UV-A intensities of 15 mW/cm2 and an air flow rate of 55 m3/h, that low ppmv levels of BTEX concentrations can be reduced to below detectable levels. Solid-phase microextraction technique was employed to monitor the levels of BTEX in the test chamber throughout the photocatalytic oxidation, lasting approximately 21 h. Destruction of BTEX from the gas phase was observed in the following sequence: o-xylene, ethylbenzene, toluene, and benzene. This study identified sequential degradation of BTEX, in combination with the stringent regulatory level set for benzene, resulted in the air quality hazard indexes (Total Hazard Index and Hazard Quotient) remaining relatively high during the process of photocatalytic oxidation. In the practical application of photocatalytic purification, it is crucial to account for the slower oxidation kinetics of benzene. This is of particular importance due to not only its extremely low exposure limits, but also due to the classification of benzene as a Group 1 carcinogenic compound by the International Agency for Research on Cancer (IARC). Our study underscores the importance of taking regulatory considerations into account when using photocatalytic purification technology.

YUMUŞAK BEYAZ PEYNİR SALAMURASINDA KULLANILAN STABİLİZÖRLERİN PEYNİRLERİN AROMA PROFİLİ ÜZERİNE ETKİLERİ

This paper describes the compositional characterization of cheese brine and aroma profile of Soft White cheese which contains different stabilizers such as sodium caseinate, carrageenan and guar gum in the brine solutions. During the 60-day storage period, pH, titration acidity, dry matter, fat, salt and protein amounts of cheese brines were analyzed. The aroma profile of the cheese samples was examined by gas chromatography–mass spectrometry using a solid-phase microextraction technique and the proportional distribution of volatile compounds was revealed. The stabilizers in the brine increased the dry matter content in the cheese mass by binding the water and reduced salt penetration into the cheese mass. A total of 23 aromatic compounds were identified including 4 aldehydes, 5 alcohols, 4 esters, 1 ether, 5 hydrocarbons, 2 ketones and 2 organic acids in cheeses. Carrageenan and guar gum were found more effective than sodium caseinate in terms of flavor retention.

Ruthenium nanoparticles encrusted with nitrogen & sulphur magnetic quantum dots as an efficient electrochemical sensor for simultaneous determination of itraconazole and terbinafine; a dual regimen for black fungus: Magnetic solid phase micro-extraction for urine and plasma analysis

After COVID-19 pandemic, Mucormycosis (black fungus) spreads as one of its related complications, due to the decrease in immunity system after administration of COVID-19 treatment drugs. A combination therapy of Itraconazole (ITR) and Terbinafine (TEB) was proved to be effective for treatment of black fungus. A novel electrochemical sensor was designed for estimation of ITR & TEB simultaneously by square wave voltammetric (SWV) technique. The sensor was fabricated using N&S-codoped magnetic quantum dots (N,S-MQDs) and ruthenium nanoparticles (Ru NPs). The fabricated sensor was characterized by cyclic voltammetry (CV), scanning electron microscope (SEM), powder X ray diffraction (pXRD), Fourier transform-Infrared (FT-IR), Raman spectroscopy and electrochemical impedance spectroscopy (EIS). Full optimization study for various experimental and instrumental parameters, in addition to method validation following International conference on Harmonization (ICH) guidelines was achieved. A good linearity in the range of 0.5–30 μg mL−1 with limit of detection (LOD) 0.24 and 0.19 μg mL−1 for ITR and TEB, respectively were obtained. The sensor was applied for analysis of ITR and TEB simultaneously in human plasma and urine samples without any interferences by applying dispersive magnetic solid phase micro-extraction (dMSPE) technique, where excellent recovery results exceeding 95 % were achieved.

Identification, semi-quantification, and dynamics of volatile organic compounds during spontaneous fermentation of two cocoa varieties from northern Peru, using HS-SPME/GC-MS techniques

During spontaneous fermentation, an important process through which cocoa beans pass, volatile organic compounds (VOCs) and non-VOCs are generated and act as precursors of aromas and flavors that influence the chocolate. In the north of Peru, cocoas of different varieties and qualities are grown, and one of the most valued is the fine aroma native cocoa (Cacao Fino de Aroma (CFA)) compared with the Castro Naranjal 51 Collection (CCN-51) variety. In this investigation, the VOCs generated during the spontaneous fermentation of CFA and CCN-51 varieties, from the department of Amazonas, Peru, were analyzed. For the extraction of VOCs, the headspace (HS) and solid-phase microextraction (SPME) techniques were used, while gas chromatography coupled to a mass spectrophotometer (GC-MS) was employed for their subsequent separation and identification. The spontaneous fermentation process lasted for 156 h, and a total of 122 VOCs were identified in 2 varieties. The dynamics of 20 VOCs were assessed, and the principal component analysis of 22 VOCs was performed to compare the profiles of VOC of the 2 cocoa varieties. In conclusion, the CFA variety presented higher concentrations of floral, fruity, and sweet aromatic VOCs that positively influence the quality of the chocolate.

The Effect of Black Garlic on the Volatile Compounds in Heat-Treated Sucuk.

This study aimed to determine the influence of using black garlic (BG) at different levels on organic volatile compounds in heat-treated sucuk (HTS), a semi dry fermented sausage. Three independent batches of sausages were prepared: control: 1% white garlic (WG): WG-1%; BG-1%: 1% BG; BG-2%: 2% BG; and BG-3%: 3% BG. After stuffing, the sausages were subjected to fermentation, heat treatment (internal temperature of 64 °C), and drying, respectively. After production, the final products were analyzed for volatile compounds. A solid-phase microextraction technique was used for the extraction of volatile compounds, and identification was carried out by a gas chromatograph/mass spectrometer. A total of 47 volatile compounds, including sulfur compounds, alcohols, esters, ketones, aliphatic hydrocarbons, acids, aromatic hydrocarbons, aldehydes, and terpenes, were identified from the sausages. The use of BG in HTS had no significant effect on aliphatic hydrocarbons, acids, ketones, aromatic hydrocarbons, and esters. BG increased the abundances of 2-propen-1-ol, allyl methyl sulfide, methyl 2-propenyl-disulfide, sabinene, β-pinene, and β-phellandrene regardless of the increase in the addition rate. BG-3% increased the level of hexanal. According to the PCA results, BG-containing groups showed positive correlation with esters, sulfur compounds, aldehydes, aromatic hydrocarbons, and alcohols, but these chemical groups were more closely correlated with BG-3%. In addition, diallyl disulfide, which is one of the main factors that causes the pungent and spicy smell of garlic, showed a close correlation with WG-1%.

Preparation of sulfonic acid functionalized covalent organic framework solid phase microextraction fibers and their application in the analysis of neurotransmitters in the mouse brain

Neurotransmitters (NTs) are essential for intercellular communication and primarily include monoamine, amino acid, and cholinergic NTs. These molecules play important roles in the body's stress response, motor coordination, neuronal communication, and homeostatic functions. Previous studies have shown that abnormal changes in NT levels are associated with various neurological disorders. Therefore, the development of accurate analytical methods for NT detection will enhance the current understanding on complex neuropathophysiology by providing functional knowledge and techniques for early diagnosis, thereby facilitating the development of new therapeutic options for the related diseases. The solid phase microextraction (SPME) technique combines sample preparation, separation, and enrichment in a single step and is minimally invasive, low cost, solvent free, and high throughput. SPME has been successfully applied to the in vivo analysis of target analytes in animal, human, and plant tissues. The coating material plays a significant role in the development of in vivo SPME methods and must meet various analytical requirements, including a suitable geometry for the SPME device, high extraction capacity, excellent selectivity, and wide extraction coverage for the target analytes. Covalent organic frameworks (COFs) are porous crystalline polymers constructed from organic framework units through strong covalent bonds; these materials are characterized with a low density, large specific surface area, permanent porosity, excellent chemical/thermal stability, and easy functionalization.In this study, a sulfonic acid-functionalized COF material (COF-SO3H) with good crystallinity, excellent chemical/thermal stability, strong hydrophobicity, a uniform mesoporous structure, and narrow pore size distribution was prepared using 2,4,6-triformylphloroglucinol and 1,4-diamino-2-nitrobenzene as monomers. Then, the COF-SO3H was coated onto the surface of stainless-steel fibers and used for in vivo enrichment of NTs. The structural properties of COF-SO3H were characterized using various techniques, such as scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR), and X-ray diffraction (XRD), all of which showed that COF-SO3H had a good crystalline structure and uniform mesopore distribution with a specific surface area of 46.17 m2/g. Compared with the SPME fibers of HLB, C18, MCX, amino, and PXC columns, the prepared COF-SO3H fibers showed better extraction efficiency for the target NTs. Next, the factors affecting SPME efficiency were optimized. The optimal desorption solvent was formic acid-methanol-water (0.5∶49.5∶50, v/v/v), and the optimal extraction and desorption times were 15 min. A method for the in vivo analysis of NTs in the brains of mice was established by combining the COF-SO3H fibers with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) under optimal conditions. The NTs were separated on an Acquity UPLC BEH-C18 analytical column (100 mm×2.1 mm, 1.7 μm) with 0.1% formic acid aqueous solution (A) and acetonitrile (B) as the mobile phases. The flow rate was set to 0.2 mL/min, and the gradient elution procedure was as follows: 0-4 min, 5%B-6%B; 4-7 min, 6%B-5%B; 7-11 min, 5%B. Under optimal conditions, the method showed good linearity (r2>0.99). The limits of quantification (S/N≥5) were in the range of 0.003-0.005 μg/mL and 3-5 μg/mL for monoamine and amino acid NTs, respectively, with RSDs of less than 20%. The method showed good precision (0.80%-9.70%) and accuracy (2.08%-17.72%), with absolute matrix effects in the range of 82.22%-117.92%. These values reflect the good purification and enrichment abilities of the proposed fibers for the target analytes. Finally, the established SPME method was combined with UPLC-MS/MS and successfully applied to quantify target NTs in the brains of mice. The proposed strategy provides a practical method for the in vivo detection and quantitative analysis of NTs and expands the applications of functionalized COF materials for the analysis of various targets.

Solid-Phase Microextraction Techniques and Application in Food and Horticultural Crops.

Solid-phase microextraction (SPME) is a sample preparation technique which utilizes small amounts of an extraction phase for the extraction of target analytes from investigated sample matrices. Its simplicity of use, relatively short sample processing time, and fiber reusability have made SPME an attractive choice for many analytical applications. SPME has been widely applied to the sampling and analysis of environmental, food, aromatic, metallic, forensic, and pharmaceutical samples. Solid phase microextraction is used in horticultural crops, for example, to determine water and soil contaminants (pesticides, alcohols, phenols, amines, herbicides, etc.). SPME is also used in the food industry to separate biologically active substances in food products for various purposes, for example, disease prevention, determining the smell of food products, and analyzing tastes. SPME has been applied to forensic analysis to determine the alcohol concentration in blood and that of sugar in urine. This method has also been widely used in pharmaceutical analysis. It is a solvent-free sample preparation technique that integrates sampling, isolation, and concentration. This review focuses on recent work on the use of SPME techniques in the analysis of food and horticultural crops.

Hierarchical covalent organic framework hollow nanofibers-bonded stainless steel fiber for efficient solid phase microextraction

The solid phase microextraction (SPME) technique has been widely applied in the detection of trace compounds in food, environment, and medicine due to its advantages of easy quantification, simple operation, and greenness. Herein, a templating strategy with SiO2 nanofibers (SiO2 NFs) is reported to synthesize hierarchical covalent organic framework hollow nanofibers (COF HNFs)-coated stainless steel fiber for SPME application with dramatically enhanced enrichment performance for trace analytes. The construction of hierarchical porosity inside the microextraction coatings can not only increase the specific surface area of COF extraction materials for obtaining more abundant adsorption sites but also greatly improve the accessibility of internal COF micropores. Moreover, the thicknesses of the microextraction COF coatings can be facilely tailored by adjusting the amount of SiO2 NFs pre-assembled on the SPME fibers. On the headspace solid phase microextraction (HS-SPME) of antimicrobial residues, the developed COF TpBD-Me2 HNFs-12 fibers achieve enrichment factors of 2026 and 1823 for thymol and carvacrol respectively, which are significantly higher than those obtained from the counterpart COF TpBD-Me2-bonded fiber (8.5–8.2 times) and commercial CAR/PDMS fiber (3.3–4.4 times). Furthermore, the developed method was demonstrated to have wide linearity (0.1–50 μg L-1), low limits of detection (0.010 μg L-1), good thermal stability and excellent reusability (>60 recycles), demonstrating great application potential in the extraction of trace organic pollutants. The strategy developed in this work is applicable to preparing a variety of topological COF (e.g., TpBD, TpPa-1) HNFs-bonded fibers.

Milk volatilome as affected by somatic cell count in Holstein cows

The aim of the current trial was to study the impact of a high somatic cell count (SCC) on milk volatilome of fresh raw milk, and its evolution during storage of processed fluid milk. Six Holstein cows were selected from our research dairy herd based on test-day SCC records. Three cows were used to produce low-SCC milk (20 × 103 cells/mL). The three other cows had one-quarter infected by Staphylococcus aureus. Infected and healthy udder halves were milked separately, and high-SCC milk was standardized to 400 × 103 cells/mL by mixing these two milks. The profile of milk volatile organic compounds (VOCs) was determined on raw milk and during the storage of processed milk. The processing included a standardization to 3.25% fat, followed by homogenization, and thermization (65 °C/30 min). This procedure was repeated four times over a period of 7 days. A total of 40 VOC were identified using the solid-phase microextraction technique followed by gas chromatography separation, mass spectrometry analysis, and database search. These VOC were grouped into seven different families, including alcohols (n = 4), free fatty acids (n = 5), sulfur compounds (n = 3), esters (n = 7), ketones (n = 7), aldehydes (n = 12), and aromatic hydrocarbons (n = 2). In raw milk, high SCC was associated with a tendency for lower concentrations of ethyl-hexanoate (P = 0.07), acetone (P = 0.06), and benzaldehyde (P = 0.07) and lower concentrations of trans-2 hexenal (P = 0.04). On the contrary, high SCC was associated with a tendency for greater concentrations of acetic acid (P = 0.09) and hexanoic acid (P = 0.07) and greater concentrations of 2-nonanone (P = 0.02) and pentanal (P = 0.01). Concentrations of most VOC increased during the storage of processed milk. Lower concentrations of butanoic acid (P = 0.09; tendency) and ethyl hexanoate (P = 0.04), and greater concentration of 1-ocen-3-ol (P < 0.01) were observed in high-SCC milk at all times of storage evaluated. Increases in concentrations over time were less pronounced for ethanol (P < 0.01), ethyl butanoate (P = 0.05), and propanal (P = 0.10) in high SCC as compared with low SCC milk. In conclusion, an increase in SCC has a limited effect on milk volatilome, when a SCC standard of 400 × 103 cells/mL for bulk milk is respected.

Green, mildly synthesized bismuth-based MOF for extraction of polar glucocorticoids in environmental water

The complex sample matrix and low environmental concentration make it challenging to effectively determine the polar glucocorticoids. In particular, a green, economical, and environmentally friendly method is urgently needed, since a large amount of extraction solvents, samples, and extraction materials have been commonly used to improve the sensitivity of the reported methods. In this study, a green and robust phenol and bismuth-based MOF of SU101 was mildly synthesized and fabricated as a brand new solid-phase microextraction (SPME) fiber. Only tiny amounts of SU101 and desorption solvents were employed to realize the high-efficiency enrichments of glucocorticoids from water samples. The detection performance of proposed SU101 fiber towards glucocorticoids was much superior to the single-component and multi-component commercial fibers. It indicated that SU101 fiber could be an excellent candidate for the enrichments of polar pharmaceuticals. After it was coupled with the instrument of high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS), the linear range of 5–10000 ng L−1 with detection limits low to 0.070–1.5 ng L−1 and satisfactory recoveries were achieved by the developed method. Benefiting from the environmental friendliness of SU101 and the less-solvent consumption of SPME technique, this work presented a green and economical strategy for determinations of trace glucocorticoids.

Analysis of Volatile Constituent by Hydrodistillation and Solid-Phase Microextraction Techniques and Antimicrobial and Scolicidal Activities of Essential Oil and Soxhlet Extracts of Ulva rigida grown in Turkey.

In the present study, the volatile composition of Ulva rigida (U. rigida) was elucidated by two different methods. As a result of the identification process of volatile components using the GC/MS-FID instrument, 31 compounds were identified by hydrodistillation (HD) method, and 15 compounds were identified by solid-phase microextraction (SPME) method, elucidating the structure of 99.86 % and 92.65 %, respectively. The most abundant compounds in the essential oil of U. rigida were n-hexadecanoic acid and pentadecanal, while the most abundant compound according to the SPME analysis was heptadecyne, a hydrocarbon compound. In the next step, hexane, dichloromethane, chloroform and methanol solvent extracts of U. rigida were prepared and the antimicrobial activities of the extracts and the essential oil obtained by hydro-distillation as well as the scolicidal activities of the solvent extracts were determined. The results of the antimicrobial activity test of the essential oil showed a high level of activity against Bacillus cereus ATCC 10876 and MRSA. The highest activity was found on the microorganism of Pseudomonas aeruginosa ATCC 9027 in chloroform and methanol extracts of U. rigida. Furthermore, viability detection was performed and the scolicidal effects of the extracts on protoscoleces were assessed. The values of lethal concentration doses (LD50 , LD75 and LD90 ) were calculated using probit analysis.

Optimization and synthesis of a novel sorbent composite based on magnetic chitosan-amine-functionalized bimetallic MOF for the simultaneous dispersive solid-phase microextraction of four aflatoxins in real water, herbal distillate, and food samples.

Aflatoxins (AFs), an important category of pollutants, are formed in many foods and adversely affect human health. Therefore, their determination is critical to ensuring human food health. An efficient dispersive solid-phase microextraction technique was developed as a simple and straightforward sample preparation technique for determination of four aflatoxins using a high-performance liquid chromatography (HPLC) fluorescence detector. A novel efficient, green sorbent for extracting AFs was synthesized based on hydrothermal and chemical strategies. The amounts of three sorbent components were optimized using a mixture design (simplex lattice design), including 14 experiments. The optimal amount of amino-bimetallic Fe/Ni-MIL-53 nanospheres, chitosan, and magnetic Fe3O4 nanoparticles as sorbent components was 0.87, 0.67, and 0.47 g, respectively. Also, various factors affecting the process of AF determination were studied and optimized in two successive experimental designs, including the definitive screening design and the Box-Behnken design. Under optimal conditions, the linear ranges for measuring aflatoxin B1, aflatoxin B2, aflatoxin G1, and aflatoxin G2 were 0.05-82.6, 0.07-86.4, 0.08-85.7, and 0.07-89.5 ng mL-1, respectively. The relative standard deviations under inter-day and intra-day conditions for measuring AFs at three analyte concentrations were determined in triplicate analysis and were in the ranges of 3.7-4.6% and 4.9-6.1% for water sample analysis, respectively. The qualitative detection limits for determining AFs were between 0.01 and 0.05 ng mL-1. The pre-concentration factor of the method for measuring AFs ranged from 739.7 to 802.1. The proposed method was used for determining AFs in several real samples, including herbal distillate, black tea, corn, and real water samples. The relative recovery and standard deviation were 87.8-97.8% and 4.10-6.82%, respectively.

Cork Sheet as an Efficient Biosorbent forForensic Toxicology: Application to Vitreous Humor Analysis.

There is an increasing number of people affected worldwide by mental health disorders, such as depression and anxiety. One of the main courses of treatment, along with psychotherapy, is the use of psychoactive medications, like antidepressants and benzodiazepines. Also, the unprescribed use of these substances is a concerning public health issue. Hence, the analysis of psychotropic medications is mandatory in postmortem toxicology and various biological samples can be used for this detection, among them the vitreous humor (VH) stands out. Also, there is a demand for more sustainable and more efficient extraction methodologies according to green chemistry. An example is solid phase microextraction techniques (SPME), which use a solid sorbent and small solvent amounts. Biosorbents are substances of natural origin with sorptive properties, and they have been successfully used in SPME in environmental toxicology for water analysis, mainly. This study aimed to develop a sustainable, fast, cheap and simple SPME methodology using cork sheet strips as a biosorbent, to extract antidepressants, benzodiazepines and others from VH samples by liquid chromatography coupled to tandem mass spectrometry. The extraction was conducted in a 96-well plate using 200 µL of VH and optimization of relevant parameters for extraction was performed. For solvent optimization, two simplex-centroid experiments were planned for extraction and desorption and to evaluate time and pH, a Doehlert design experiment was performed. The analytical method for the determination and quantification of 17 substances was validated. The quantification limits were 5 ng/mL for all analytes and the calibration curves were linear between 5 and 30 ng/mL. This study was able to develop an efficient, cheap, simple and fast microextraction method for 17 analytes in VH, using strips of cork sheet for extraction and a 96-well plate as a container. Furthermore, this approach system could be automated for routine toxicology laboratories.