Deep eutectic solvent-based shaking-assisted extraction for determination of bioactive compounds from Norway spruce roots.

Polyphenolic compounds play an essential role in plant growth, reproduction, and defense mechanisms against pathogens and environmental stresses. Extracting these compounds is the initial step in assessing phytochemical changes, where the choice of extraction method significantly influences the extracted analytes. However, due to environmental factors, analyzing numerous samples is necessary for statistically significant results, often leading to the use of harmful organic solvents for extraction. Therefore, in this study, a novel DES-based shaking-assisted extraction procedure for the separation of polyphenolic compounds from plant samples followed by LC-ESI-QTOF-MS analysis was developed. The DES was prepared from choline chloride (ChCl) as the hydrogen bond acceptor (HBA) and fructose (Fru) as the hydrogen bond donor (HBD) at various molar ratios with the addition of 30% water to reduce viscosity. Several experimental variables affecting extraction efficiency were studied and optimized using one-variable-at-a-time (OVAT) and confirmed by response surface design (RS). Nearly the same experimental conditions were obtained using both optimization methods and were set as follows: 30 mg of sample, 300 mg of ChCl:Fru 1:2 DES containing 30% w/w of water, 500 rpm shaking speed, 30 min extraction time, 10°C extraction temperature. The results were compared with those obtained using conventional solvents, such as ethanol, methanol and water, whereby the DES-based shaking-assisted extraction method showed a higher efficiency than the classical procedures. The greenness of the developed method was compared with the greenness of existing procedures for the extraction of polyphenolic substances from solid plant samples using the complementary green analytical procedure index (ComplexGAPI) approach, while the results for the developed method were better or comparable to the existing ones. In addition, the practicability of the developed procedure was evaluated by application of the blue applicability grade index (BAGI) metric. The developed procedure was applied to the determination of spruce root samples with satisfactory results and has the potential for use in the analysis of similar plant samples.

Assessment of baby disposable diapers application for urine collection and determination of phthalate metabolites.

The baby disposable diapers were investigated as a sampling material for urine collection and validated for the evaluation of the exposure of children to xenobiotics. Phthalate metabolites detected in urine samples were chosen as proof-of-concept analytes. For the determination of phthalate metabolites in children's urine samples, high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) was used. Two sampling approaches were compared, namely sterile containers and baby disposable diapers. Thirty urine samples from infants and toddlers were analyzed by both methods in parallel and the results were compared. It was found that for diaper sampling, lower concentrations of the metabolites were observed, however, the general distribution for particular metabolites remains the same for both methods. For most of the metabolites high determination coefficients were obtained, namely 0.9929 for MEHHP, 0.9836 for MMP, 0.9796 for MECPP, and 0.9784 for 2-cx-MMHP. For MEOHP the determination correlation coefficient was 0.9154, while for MBP was - 0.7771 and MEHP was - 0.5228. In general, for diaper sampling an underestimation for 2-cx-MMHP and MEOHP was observed, while for MMP diaper-based approach provides overestimation. However, the proposed procedure confirms the possibility of using baby disposable diapers as a material for the collection of urine samples for biomonitoring purposes and fast screening of phthalates exposure.

How pesticides affect neonates? - Exposure, health implications and determination of metabolites.

This review covers key information related to the effects of pesticides on fetal and child health. All humans are exposed to environmental toxicants, however child's health, due to their high vulnerability, should be of special concern. They are continuously exposed to environmental xenobiotics including a wide variety of pesticides, and other pollutants. These compounds can enter the child's body through various routes, both during fetal life, in the first days of life with breast milk, as well as during environmental exposure in later years of life. Consequently, in the body, some of them are metabolized and excreted with urine or faces, while others accumulate in tissues causing toxic effects. This review will provide information on the types of pesticides, their pathways of uptake and metabolism in children's bodies. Determination of the impact of them on children's organism performance is possible through effective identification of these compounds and their metabolites in children's tissues and biofluids. Therefore, the main procedures for the determination of pesticides are reviewed and future trends in this field are indicated. We believe that this comprehensive review can be a good starting place for the future readers interested in the impact of environmental xenobiotics on the health of children as well as the aspects relates with the analytical methods that can be used for analysis and monitoring of these pollutants in children's tissues and biofluids.

Understanding the early-stage release of volatile organic compounds from rapeseed oil during deep-frying of tubers by targeted and omics-inspired approaches using PTR-MS and gas chromatography.

During deep-frying, a plethora of volatile products is emitted with the fumes. These compounds could act as oil quality indicators and change the indoor air composition leading to health risks for occupants. The presented experiments focus on deep-frying of different tubers in rapeseed oil at different frying temperatures. Here, two scenarios for real-time monitoring of volatile organic compounds (VOCs) using proton transfer reaction mass spectrometry (PTR-MS) were proposed. The first, targeted, involved the application of gas chromatography with a flame ionization detector (GC-FID). The second, omics-inspired, involved the use of solid-phase microextraction (SPME) along with gas chromatography-mass spectrometry (GC-MS) and molecular networking algorithm as a complementary tool to the PTR-MS analysis. In a targeted approach, it was shown that the emission profile of pentanal and hexanal depends on the frying temperature and as the temperature increases, a sudden release of these compounds can be observed in the first minutes of frying. Meanwhile, using an omics-inspired protocol enables finding the relation between 1,4-heptadienal and 2-heptanone, octanal and limonene emissions. Using both approaches it was possible to record real-time changes in emission profiles of various oils' degradation products. It was also observed that the emission profiles of VOCs are strictly related to the frying temperature and the type of fried tuber.

Real-time monitoring of the emission of volatile organic compounds from polylactide 3D printing filaments.

Establishing the emission profile of volatile organic compounds generated during fused deposition modeling 3D printing using polymer filaments is important in terms of both understanding the processes taking place during thermal degradation of thermoplastics, and assessing the user's exposure to potentially harmful volatiles. However, obtaining detailed, real-time qualitative and quantitative results poses a challenge. In this paper solid-phase microextraction-gas chromatography-time-of-flight mass spectrometry and proton transfer reaction time-of-flight mass spectrometry were used to identify and monitor the emission of volatiles during thermal degradation of polylactide filaments and during 3D printing. Filaments of two different grades and three colours were used. It was possible to obtain detailed, time- and temperature-resolved emission profiles of the main products of thermal decomposition of lactide and polylactide 3D printing filaments at concentration levels of a few µg/g. This revealed different temperature-dependent emission characteristics of particular volatiles, such as, among others, lactide, acetaldehyde, acetic acid, and 2-butanone between various polylactide 3D printing filaments. This approach can be used to monitor the emission associated with printing with various other types of polymer 3D printing materials.

Revealing dynamic changes of the volatile profile of food samples using PTR-MS.

Volatile compounds carry valuable information regarding the properties of foodstuffs. Volatiles emitted from food can be used as, for example, indicators of quality, shelf-life, or authenticity. A better understanding of the multitude of transformations which occur during food processing could facilitate the optimisation of production, increase the desirability of food products, and also their wholesomeness. However, as some of these transformations are fast-paced, it is necessary to monitor them using techniques which enable real-time determination of volatiles, such as proton transfer reaction-mass spectrometry (PTR-MS). Recent years have seen a marked increase in its use in food analysis, since it can be used to obtain insight into the dynamics of the monitored processes and can be the basis for precise quality control methods for food processing. This review highlights recent works in which PTR-MS was used in monitoring during foodstuffs production, preparation and storage.

Release Kinetics Studies of Early-Stage Volatile Secondary Oxidation Products of Rapeseed Oil Emitted during the Deep-Frying Process.

The research concerns the use of proton transfer reaction mass spectrometer to track real-time emissions of volatile secondary oxidation products released from rapeseed oil as a result of deep-frying of potato cubes. Therefore, it was possible to observe a sudden increase of volatile organic compound (VOC) emissions caused by immersion of the food, accompanied by a sudden release of steam from a potato cube and a decrease of the oil temperature by more than 20 °C. It was possible to identify and monitor the emission of major secondary oxidation products such as saturated and unsaturated aldehydes, namely acrolein, pentanal, 2-hexenal, hexanal, 2-nonenal and 2-decenal. Each of them has an individual release characteristic. Moreover, the impact of different initial frying temperatures on release kinetics was investigated. Subsequently, it was possible to approximate the cumulative emission by a second-degree polynomial (R2 ≥ 0.994). Using the proposed solution made it possible for the first time to observe the impact of the immersion of food in vegetable oil on the early emission of thermal degradation products oil.

Real-Time Volatilomics: A Novel Approach for Analyzing Biological Samples.

The use of the 'omics techniques in environmental research has become common-place. The most widely implemented of these include metabolomics, proteomics, genomics, and transcriptomics. In recent years, a similar approach has also been taken with the analysis of volatiles from biological samples, giving rise to the so-called 'volatilomics' in plant analysis. Developments in direct infusion mass spectrometry (DI-MS) techniques have made it possible to monitor the changes in the composition of volatile flux from parts of plants, single specimens, and entire ecosystems in real-time. The application of these techniques enables a unique insight into the dynamic metabolic processes that occur in plants. Here, we provide an overview of the use of DI-MS in real-time volatilomics research involving plants.

Key-Marker Volatile Compounds in Aromatic Rice (Oryza sativa) Grains: An HS-SPME Extraction Method Combined with GC×GC-TOFMS.

The aroma of rice essentially contributes to the quality of rice grains. For some varieties, their aroma properties really drive consumer preferences. In this paper, using a dynamic headspace solid-phase microextraction (HS-SPME) system coupled to a two-dimensional gas chromatography (GC×GC) using a time-of-flight mass spectrometric detector (TOFMS) and multivariate analysis, the volatile compounds of aromatic and non-aromatic rice grains were contrasted to define some chemical markers. Fifty-one volatile compounds were selected for principal component analysis resulting in eight key-marker volatile compounds (i.e., pentanal, hexanal, 2-pentyl-furan, 2,4-nonadienal, pyridine, 1-octen-3-ol and (E)-2-octenal) as responsible for the differences between aromatic and non-aromatic rice varieties. The factors that are most likely to affect the HS-SPME efficiency for the aforementioned key-marker compounds were evaluated using a 2 I I I 5 - 2 fractional factorial design in conjunction with multi-response optimisation. The method precision values, expressed as % of coefficient of variation (CV), were ranging from 1.91% to 26.90% for repeatability (n = 9) and 7.32% to 37.36% for intermediate precision (n = 3 × 3). Furthermore, the method was successfully applied to evaluate the volatile compounds of rice varieties from some Asian countries.

Prediction of the Biogenic Amines Index of Poultry Meat Using an Electronic Nose.

The biogenic amines index of fresh chicken meat samples during refrigerated storage was predicted based on the headspace analysis using an electronic nose equipped with an array of electrochemical sensors. The reference biogenic amines index values were obtained using dispersive liquid⁻liquid microextraction⁻gas chromatography⁻mass spectrometry. A prototype electronic nose with modular construction and a dedicated sample chamber was used to rapidly analyze the volatile fraction of chicken meat samples, with a single measurement time of five minutes. Back-propagation artificial neural network was used to estimate the biogenic amines index of the samples with a determination coefficient of 0.954 based on ten-fold stratified cross-validation. The results indicate that the determination of the biogenic amines index is a good reference method for studies in which the freshness of meat products is assessed based on headspace analysis and fingerprinting, and that the described electronic device can be used to assess poultry meat freshness based on this value with high accuracy.

Direct determination of cadaverine in the volatile fraction of aerobically stored chicken breast samples.

ABSTRACT: To supplement the currently used methods for poultry meat shelf life assessment, it might be necessary to develop a technique for rapid headspace analysis of volatiles with no prior sample preparation step. Biogenic amines, in particular cadaverine, are considered meat spoilage indicators. Described in this article are the results of a preliminary investigation of the applicability of proton transfer reaction mass spectrometry in the determination of cadaverine concentration in the volatile fraction of poultry meat samples stored in aerobic conditions. Dispersive liquid-liquid microextraction-gas chromatography-mass spectrometry and determination of total viable bacteria were used as reference methods. It was determined that there is a good correlation (Pearson correlation of 0.96) between the concentration of cadaverine in the headspace of chicken meat samples stored over a period of 5 days and the total viable bacteria count. Based on the results, it can be concluded that the changes of cadaverine concentration in the meat samples' volatile fraction can be successfully monitored with a short time of a single analysis and with no sample preparation.

A new method for real-time monitoring of volatiles in frying fumes using proton transfer reaction mass spectrometry with time-of-flight analyser.

ABSTRACT: To safeguard the consumers' well-being, it is necessary to develop novel methods for determination of carcinogens in food, including volatiles generated during frying. The currently used procedures for analysis of volatile fraction of vegetable oils are not based on real-time measurements and thus do not enable the determination of carcinogenic compounds in frying fumes; instead, only the headspace or liquid fraction is sampled. In this article, described is an approach in which proton transfer reaction mass spectrometry with time-of-flight analyser (PTR-TOFMS) was used for real-time monitoring of carcinogenic compounds generated during thermal degradation of rapeseed oil. Using PTR-MS, it was possible to monitor the concentration of known volatile carcinogens according to the International Agency for Research on Cancer (IARC), alongside BTEX compounds, acrolein, and selected aldehydes. Moreover, the applicability of several supervised data analysis methods for the classification of oil samples according to their degree of thermal degradation was presented, with best results obtained using the k-nearest neighbours algorithm. Proton transfer reaction mass spectrometry is a powerful technique for the determination of carcinogenic compounds generated during thermal degradation of edible oils. Further investigation of the chemical processes which occur during frying can lead to improvement of food safety.

PTR-MS and GC-MS as complementary techniques for analysis of volatiles: A tutorial review.

This tutorial review is a critical commentary on the combined use of two instrumental analytical techniques, namely GC-MS and PTR-MS. The first mention of such an analytical approach likely appeared after the year 2000 and despite many advantages, it has not been applied very often. Therefore, the aim of this article is to elaborate on the concept of their combined use and to provide a curse tutorial for those considering taking such an approach. The issue of complementarity was raised in a broad sense of this term. Special emphasis was placed on indicating the possibilities of complementary utilization of GC-MS and PTR-MS and presenting the advantages and disadvantages as well as the current application of these techniques when used together.

Electronic noses in classification and quality control of edible oils: A review.

The growing demand for wholesome and nutritious food leads to intensification of production, which in turn can have a detrimental effect on quality and well-being of consumers. For that reason, it is important to develop novel methods of food control which would be characterized by a short time of analysis, adequate sensitivity and relatively low cost. One such technique involves the use of multi-sensory devices called electronic noses. In recent years there has been a rapid development of this method, especially in the area of food control. Electronic olfaction can be successfully used in the analysis of edible oils, in particular in the determination of the product's geographical origin, and in detection of adulteration as well as deterioration caused by external factors.

Portable Electronic Nose Based on Electrochemical Sensors for Food Quality Assessment.

The steady increase in global consumption puts a strain on agriculture and might lead to a decrease in food quality. Currently used techniques of food analysis are often labour-intensive and time-consuming and require extensive sample preparation. For that reason, there is a demand for novel methods that could be used for rapid food quality assessment. A technique based on the use of an array of chemical sensors for holistic analysis of the sample's headspace is called electronic olfaction. In this article, a prototype of a portable, modular electronic nose intended for food analysis is described. Using the SVM method, it was possible to classify samples of poultry meat based on shelf-life with 100% accuracy, and also samples of rapeseed oil based on the degree of thermal degradation with 100% accuracy. The prototype was also used to detect adulterations of extra virgin olive oil with rapeseed oil with 82% overall accuracy. Due to the modular design, the prototype offers the advantages of solutions targeted for analysis of specific food products, at the same time retaining the flexibility of application. Furthermore, its portability allows the device to be used at different stages of the production and distribution process.

Different Ways to Apply a Measurement Instrument of E-Nose Type to Evaluate Ambient Air Quality with Respect to Odour Nuisance in a Vicinity of Municipal Processing Plants.

This review paper presents different ways to apply a measurement instrument of e-nose type to evaluate ambient air with respect to detection of the odorants characterized by unpleasant odour in a vicinity of municipal processing plants. An emphasis was put on the following applications of the electronic nose instruments: monitoring networks, remote controlled robots and drones as well as portable devices. Moreover, this paper presents commercially available sensors utilized in the electronic noses and characterized by the limit of quantification below 1 ppm v/v, which is close to the odour threshold of some odorants. Additionally, information about bioelectronic noses being a possible alternative to electronic noses and their principle of operation and application potential in the field of air evaluation with respect to detection of the odorants characterized by unpleasant odour was provided.

Thermal degradation assessment of canola and olive oil using ultra-fast gas chromatography coupled with chemometrics.

ABSTRACT: Oil blending is often used to enhance the properties of vegetable oils. The admixture of a more thermally stable oil makes the resulting blend more suitable for use in frying. A new method of quality assessment of vegetable oils used in frying is presented in this paper. In this method, ultra-fast gas chromatography coupled with flame ionization detector and chemometrics is employed. Principal component analysis was used for data processing. The results obtained with this method were compared with the results of the Rancimat test and sensory evaluation. It is demonstrated that the addition of olive oil improves the stability of rapeseed oil, and also changes its flavour and aroma profile. In addition, it was found that ultra-fast GC coupled with chemometrics is an effective tool for the assessment of the quality of edible oils. The proposed method does not require sample preparation, and the total time of analysis is less than 2 min.

Poultry meat freshness evaluation using electronic nose technology and ultra-fast gas chromatography.

ABSTRACT: To ensure that chicken meat products are safe to consume, it is important to be able to reliably determine its shelf-life. To assess the applicability of ultra-fast gas chromatography and electronic nose technology in evaluation of poultry, an analysis of the headspace of ground chicken meat samples refrigerated over a period of 7 days was performed. Chemometric techniques were used to mine additional information from a multiparametric data set. As a reference, sensory evaluation was also conducted, and several volatile chemical compounds that can potentially be used as poultry meat decomposition indicators were identified. The obtained results suggest the possibility of using both techniques to supplement the established methods of chicken meat quality assessment.

Dynamic Headspace Sampling as an Initial Step for Sample Preparation in Chromatographic Analysis.

This work represents a brief summary of the use of dynamic headspace (DHS) as a technique for sample preparation in chromatographic analysis. Despite numerous developments in the area of analyte isolation and enrichment, DHS remains one of the fundamental methods used with GC. In our opinion, interest in this technique will not diminish significantly because it conforms to stipulations of green analytical chemistry. Moreover, DHS fulfills the need for methods that facilitate detection and determination of analytes present at ultratrace levels in complex matrixes. The main focus of this work was placed on the theoretical fundamentals of this method. Also described herein were DHS development, the advantages and disadvantages of this technique compared with other headspace sampling techniques, and selected examples of its applications in food and environmental analyses.