Comment on Tremmel et al. In Vitro Metabolism of Six C-Glycosidic Flavonoids from Passiflora incarnata L. Int. J. Mol. Sci. 2021, 22, 6566.

In recent years, growing attention has been paid to the chemical composition of aerial parts extracts and the bioavailability of active compounds from different species of Passiflora genus [...].

Ethoxylated Butoxyethanol-BADGE Adducts-New Potential Migrants from Epoxy Resin Can Coating Material.

The acetonitrile extracts of can-coating materials have been analyzed by using high-pressure liquid chromatography/electrospray ionization-mass spectrometry (HPLC/ESI-MS). On the basis of detected ions [M + H]+, [M + NH4]+, [M + Na]+ and product ions, the ethoxylated butoxyethanol-bisphenol A diglycidyl ether adducts were identified in two of the analyzed extracts. Although the oxyethylene unit-containing compounds are widely used for the production of different kinds of materials, the ethoxylated species have not been earlier detected in epoxy resin can-coatings.

The Presence of Mycotoxins in Human Amniotic Fluid.

Mycotoxin exposure assessments through biomonitoring studies, based on the analysis of amniotic fluid, provides useful information about potential exposure of mothers and fetuses to ubiquitous toxic metabolites that are routinely found in food and the environment. In this study, amniotic fluid samples (n = 86) were collected via abdominal amniocentesis at 15-22 weeks of gestation from pregnant women with a high risk of chromosomal anomalies or genetic fetal defects detected during 1st trimester prenatal screening. These samples were analyzed for the presence of the most typical Aspergillus, Penicillium and Fusarium mycotoxins, with a focus on aflatoxins, ochratoxins and trichothecenes, using the LC-FLD/DAD method. The results showed that the toxin was present in over 75% of all the tested samples and in 73% of amniotic fluid samples from fetuses with genetic defects. The most frequently identified toxins were nivalenol (33.7%) ranging from

2,2-Bis(4-Hydroxyphenyl)-1-Propanol-A Persistent Product of Bisphenol A Bio-Oxidation in Fortified Environmental Water, as Identified by HPLC/UV/ESI-MS.

Biodegradation of bisphenol A in the environmental waters (lake, river, and sea) has been studied on the base of fortification of the samples taken and the biodegradation products have been analyzed using HPLC/UV/ESI-MS. Analysis of the characteristic fragmentation patterns of [M-H]- ions permitted unambiguous identification of the biodegradation products as 2,2-bis(4-hydroxyphenyl)-1-propanol or as p-hydroxyacetophenone, depending on the type of surface water source. The formation of 2,2-bis(4-hydroxyphenyl)-1-propanol was much more common than that of p-hydroxyacetophenone. Moreover, 2,2-Bis(4-hydroxyphenyl)-1-propanol has not been further biodegraded, in contrast to the p-hydroxyacetophenone, which was further mineralized. It has been proved, for the first time, that 2,2-bis(4-hydroxyphenyl)-1-propanol can be regarded as persistent product of bisphenol A biodegradation in the fortified environmental waters.

Elucidation of glycosylation sites of kaempferol di-O-glycosides from methanolic extract of the leaves of Prunus domestica subsp. syriaca.

RATIONALE: Flavonol glycosides containing the glycosylation patterns 3,4'-di-O and 4',7-di-O are rare in nature and they have not yet been studied in detail by electrospray ionization mass spectrometry (ESI-MS(+/-), in contrast to the flavonol glycosides containing the glycosylation pattern 3,7-di-O. METHOD: The leaves from Prunus domestica L. subsp. syriaca were extracted with pure methanol or, in order to perform hydrolysis and extraction simultaneously, with a 5% methanolic solution of hydrochloric acid. The high-performance liquid chromatography (HPLC)/ESI-MS(+/-) analyses were performed using a Waters model 2690 HPLC pump and a Waters/Micromass ZQ2000 mass spectrometer. RESULTS: Three kinds of kaempferol di-O-glycosides have been identified, namely kaempferol-3-O-hexoside-7-O-rhamnosides, kaempferol-3-O-pentoside-4'-O-rhamnosides and kaempferol 4',7-di-O-rhamnoside. The identification was performed on the basis of the abundances of the respective Y-type product ions. CONCLUSIONS: The abundances of [Yn 0 - H]-· , Yn 0 - and Yn 0 + product ions were of crucial importance for the determination of glycosylation patterns. The obtained results can be useful for HPLC/ESI-MS identification of rare flavonol-di-O-glycosides.

Differentiation of bisphenol F diglycidyl ether isomers and their derivatives by HPLC-MS and GC-MS-comment on the published data.

Positional isomers of bisphenol F diglycidyl ether (BFDGE) have been analyzed by high-pressure liquid chromatography-mass spectrometry and by gas chromatography-mass spectrometry (HPLC-MS, GC-MS). Positional isomers of BFDGE derivatives (BFDGEx2H2O, BFDGExH2OxHCl) have been analyzed by HPLC-MS. On the basis of the obtained fragmentation patterns, the elution order of the isomers has been unequivocally determined, in standard solutions and in the sample of liquid obtained after rinsing an empty mackerel fish can with acetonitrile. Under HPLC condition, para,para isomers are eluted first, then ortho,para isomers' elution follows, and ortho,ortho isomers are eluted last. Under GC condition, the reverse elution order has been obtained. For the first time, two ortho,para isomers of BFDGExH2OxHCl have been detected and their elution order has been determined. The obtained results are of key importance for determination of the isomer distribution of BFDGE and its derivatives in food samples.

Electrospray ionisation mass spectrometric behaviour of flavonoid 5-O-glucosides and their positional isomers detected in the extracts from the bark of Prunus cerasus L. and Prunus avium L.

INTRODUCTION: Literature data concerning the electrospray ionisation mass spectrometry (ESI-MS) behaviour of flavonoid 5-O-glycosides are poor and sometimes disputable. Therefore, we decided to analyse the compounds of this kind present in the bark of Prunus cerasus and Prunus avium by using high-performance liquid chromatography HPLC/ESI-MS. OBJECTIVE: The aim of this study is to obtain the comprehensive information about the ESI-MS(+/-) behaviour of flavonoid 5-O-glucosides, to compare their behaviour with that of their positional isomers, to confirm that the known susceptibility of flavonoid 5-O-glucosides to hydrolysis may be successfully used for their identification. METHOD: The bark from Prunus trees was extracted with pure methanol or, in order to perform hydrolysis and extraction simultaneously, with 5% methanolic solution of hydrochloric acid. The HPLC-ESI-MS analyses were performed using a Waters model 2690 HPLC pump and Waters/Micromass ZQ2000 mass spectrometer. RESULTS: Flavonoid 5-O-glycosides were completely hydrolysed under the acid conditions used, in contrast to their positional isomers. In positive ion mode, at low cone voltage, flavonoid 5-O-glycosides yield abundant Y0 + aglycone ions, in contrast to their positional isomers. In the negative ion mode, flavonoid 5-O-glycosides do not yield [Y0 - H]-· fragment ions, in contrast to their positional isomers. When aglycone contains only two hydroxyl groups, the flavonoid 5-O-glycosides can be detected in negative ion mode, whereas their positional isomers do not yield [M - H]- ions. CONCLUSION: It has been demonstrated that the susceptibility to hydrolysis of the analysed compounds, the abundances of respective fragment ions formed, and their ESI(-) response allow unambiguous identification of flavonoid 5-O-glycosides and their differentiation from their positional isomers.

Detection of flavone C-glycosides in the extracts from the bark of Prunus avium L. and Prunus cerasus L.

The extracts from the bark of Prunus avium and Prunus cerasus have been analyzed by using high pressure liquid chromatography/electrospray ionization mass spectrometry. For the first time in the bark of Prunus species flavonoid C-glycosides have been detected. On the basis of the characteristic fragmentation patterns of their [M-H]- and [M + H]+ ions, three flavonoid C-glycosides have been identified, namely apigenin-6,8-di-C-glucoside (vicenin-2), apigenin-6-C-glucoside (isovitexin) and chrysin-8-C-glucoside. Taking into account the widely studied biological activities of flavonoid C-glycosides, the barks of these common fruit trees seem to be interesting materials of potential medical or cosmetic application.

Comment on the published data concerning the identification of biochanin A and prunetin by LC/ESI-MS.

Biochanin A is one of the most common phytoestrogens, occurring in high concentrations in soy and red clover, for instance, which shows a wide spectrum of biological activity. Prunetin is an isomer of biochanin A, and even though it is not very common, its structural relationship to the latter makes it interesting, regarding its biological activity. Nowadays, LC/ESI-MS methods are widely used for identification of natural compounds, including biochanin A and prunetin. However, we found that the published data concerning the identification of biochanin A and prunetin are sometimes disputable. Namely, the identification is based on the product ions which cannot be regarded as characteristic of biochanin A or prunetin. The reported retention times sometimes may be also disputable.

Identification of isoflavones in the extract of supplements for menopause symptoms by direct infusion electrospray ionization tandem mass spectrometry.

In recent years high consumption of dietary supplements has been observed. However, the consumption of dietary supplements may lead to the unexpected side effects that can be related to the number of adulterated supplements quite often marketed. It has prompted the search for a fast and reliable method of identification of main active compounds in the supplements. In this study, the isoflavones present in the methanol extracts of dietary supplements for menopause symptoms were identified by using direct infusion electrospray ionization tandem mass spectrometry. The product ion spectra of [M-H]- ions derived from the extracts matched very well those obtained for standard compounds. Daidzein, genistein, and glycitein were identified in the soy-based supplements, while daidzein, formononetin, and biochanin A were identified in the red clover-based ones. The respective [M+Na]+ ions were also detected; however, their product ion spectra did not allow isoflavone identification. It can be concluded that the main isoflavones present in the extracts of dietary supplements can be successfully and quickly identified by using the direct infusion electrospray ionization in negative ion mode, followed by the tandem mass spectrometry experiment.

Signals of diagnostic ions in the product ion spectra of [M - H]- ions of methoxylated flavonoids.

RATIONALE: The main feature of the fragmentation of [M - H]- ions of methoxylated flavonoids is the loss of methyl radical (formation of the [M - H - CH3 ]-• product ion). Subsequent decomposition of [M - H - CH3 ]-• product ions may be useful for identification of a given compound by HPLC/MS. This paper describes how the selected diagnostic fragment ions can be useful during HPLC/MS(-) analysis of methoxylated flavonoids. METHODS: Product ion spectra (ESI-CID-MS/MS spectra) of [M - H]- ions of 17 methoxylated flavonoids (flavones, isoflavones and flavonols) were obtained with a Q-TOF mass spectrometer. Full scan mass spectra (ESI-MS) were obtained with a single quadrupole type of instrument. RESULTS: A number of product ions were recognized as useful from the point of view of structural elucidation. In most cases they were diagnostic product ions, formed as a result of C ring breaking. CONCLUSIONS: The most important conclusions drawn from this study are: the product ion at m/z 132 indicates that the analysed compound is an isoflavone; the product ion at m/z 117 indicates the presence of one hydroxy group at ring B or at the 3-position; biochanin A and prunetin can be differentiated by their 'in-source' fragmentation, by the relative abundances of product ions at m/z 195, 183 and 167; loss of mass 102 from the [M - H - CH3 ]-• ion indicates that ring B is not substituted and there is no hydroxy group at the 3-position; and rhamnetin can be detected using three diagnostic product ions, namely at m/z 121, 165 and 193.

Air-drying temperature changes the content of the phenolic acids and flavonols in white mulberry (Morus alba L.) leaves / Temperatura de secagem ao ar altera o teor de ácidos fenólicos e flavonóis em folhas de amoreira branca (Morus alba L.)

ABSTRACT: The white mulberry leaves are typically available on the market in dried or encapsulated form. It was assumed in the study that appropriate drying of leaves of the white mulberry is significant for obtaining intermediate products with high content of compounds having anti-oxidative activity. The purpose of the study was to determine the influence of the temperature of mulberry leaves air drying on the content of phenolic acids and flavonols. It has been determined that the content of these compounds in the leaves depended on the drying temperature. Drying at 60 °C favored release of phenolic acids and flavonols from complexes and/or formation of new compounds. Their total content was 22% higher than in leaves dried at 30 °C. Drying at 90 °C reduced the phenolic acid and flavonol content by 24%. The most favorable drying temperature was 60 °C.

RESUMO: As folhas da amoreira branca estão normalmente disponíveis no mercado em forma seca ou encapsulada. Assumiu-se no estudo que a secagem adequada das folhas da amora branca é importante para a obtenção de produtos intermediários com alto teor de compostos com atividade antioxidante. O objetivo do estudo foi determinar a influência da temperatura de secagem de ar de folhas de amoreira sobre o teor de ácidos fenólicos e flavonóis. Foi determinado que o conteúdo destes compostos nas folhas dependia da temperatura de secagem. Secagem a 60 °C favoreceu a liberação de ácidos fenólicos e flavonóis a partir de complexos e / ou formação de novos compostos. Seu teor total foi 22% superior ao das folhas secas a 30 °C. A secagem a 90 °C reduziu o teor de ácido fenólico e flavonol em 24%. A temperatura de secagem mais favorável foi de 60 °C.

Endocrine disruptor compounds in environment: As a danger for children health.

Endocrine disrupting compounds (EDCs) are heterogenous in structure and include synthetic organic compounds such as pharmaceutical agents, plant protection products, plastics, plasticizers, polychlorinated biphenyls, dioxins, flame-retardants, and antifoulant paint additive, as well, as natural plant-derived EDCs termed phytoestrogens and mycoestrogens. Children and adults are exposed daily to EDCs during drinking contaminated water, eating, breathing polluted air or direct contact with chemicals. Prenatal and perinatal period, infancy, childhood, and puberty are critical time of development during which maturing systems are particularly sensitive to hormonal disruptions (small elimination of xenobiotics). Exposure to environmental chemicals with estrogenic or antiandrogenic action may disrupt female reproductive tract development, also testosterone synthesis and sexual differentiation, leading to adult testis dysfunction and infertility. What is important, today there is still no definitive risk assessment tool for EDCs.

Zearalenone in the Intestinal Tissues of Immature Gilts Exposed per os to Mycotoxins.

Zearalenone and its metabolites, α-zearalenol and ß-zearalenol, demonstrate estradiol-like activity and disrupt physiological functions in animals. This article evaluates the carryover of zearalenone and its selected metabolites from the digesta to intestinal walls (along the entire intestines) in pre-pubertal gilts exposed to low doses of zearalenone over long periods of time. The term "carryover" describes the transfer of mycotoxins from feed to edible tissues, and it was used to assess the risk of mycotoxin exposure for consumers. The experimental gilts with body weight of up to 25 kg were per os administered zearalenone at a daily dose of 40 µg/kg BW (Group E, n = 18) or placebo (Group C, n = 21) over a period of 42 days. In the first weeks of exposure, the highest values of the carryover factor were noted in the duodenum and the jejunum. In animals receiving pure zearalenone, the presence of metabolites was not determined in intestinal tissues. In the last three weeks of the experiment, very high values of the carryover factor were observed in the duodenum and the descending colon. The results of the study indicate that in animals exposed to subclinical doses of zearalenone, the carryover factor could be determined by the distribution and expression of estrogen receptor beta.

Impact of fat and selected profiles of fatty acids contained in the colostrum and milk of sows of native breeds on piglet rearing.

The aim of this study was to evaluate the effect of the level of fat and selected fatty acids found in the milk of sows on the rearing of native breed piglets. Simultaneously, in order to improve the accuracy of the performed analyses, atomic absorption spectrometry was employed in the applied analytic methodology. The experimental animal material comprised 60 sows of the indigenous White Zlotnicka breed. Colostrum and milk were collected on the first and 14th days of lactation. In all, 240 samples were collected. The following parameters were determined in the course of the experiment: number and weight of piglets, body weight gains as well as deaths of piglets. A total of 1270 born piglets was subjected to investigations. The performed experiments demonstrated that, with the progress of the lactation period, the content of fat and saturated fatty acids (SFA) turned out to be statistically significant and showed a growing tendency. Fat increased by about 2% and palmitic acid (C16:0) increased most, that is by 5%. Linolic (C18:2) and linolenic (C18:3) acids revealed decreasing trends. Irrespective of the day of lactation, the level of unsaturated fatty acids (UFA) determined in sows' colostrum and milk was higher in comparison with that of SFA, and the UFA to SFA ratio ranged from 1.84% to 1.33%. Proportions of n-6 to n-3 fatty acids were determined at the level of about 1.6:1.0 in the colostrum and 1.3:10 in milk. The highest daily body weight gains were recorded in the case of piglets derived from sows with the highest fat level - 294 g, while in the case of stearic acid (C18:0), the smaller its concentration in the colostrum and milk of the experimental sows, the better body weight gains of piglets - 262 g. At the same time, stearic acid (C18:0) was found to exert a statistically significant effect on piglet mortality at the level of P ≤ 0.05. Its highest concentration caused the highest proportion of deaths among piglets - 16.23%. The performed analysis of correlations that occurred between fat, fatty acids and traits associated with piglet rearing confirmed that linolic acid (C18:2; n-6) was highly significantly correlated with piglets' body weights (r = 0.456**) and was negatively correlated with piglets' deaths (r = -0.312). On the other hand, fat revealed correlation with body weight gains of piglets (r = 0.333*_ and a negative correlation with deaths of piglets (r = -0344*). Recapitulating, the results of the performed experiments revealed that differences in the levels of fat and fatty acids found in sows' colostrum and milk influenced results of piglet rearing. Together with the increase in the content of fat and UFA in sows' colostrum and milk, piglets were characterized by the best body weight, growth rate, as well as by small mortality.

Deoxynivalenol in the gastrointestinal tract of immature gilts under per os toxin application.

Deoxynivalenol is also known as vomitoxin due to its impact on livestock through interference with animal growth and acceptance of feed. At the molecular level, deoxynivalenol disrupts normal cell function by inhibiting protein synthesis via binding to the ribosome and by activating critical cellular kinases involved in signal transduction related to proliferation, differentiation and apoptosis. Because of concerns related to deoxynivalenol, the United States FDA has instituted advisory levels of 5 µg/g for grain products for most animal feeds and 10 µg/g for grain products for cattle feed. The aim of the study was to determine the effect of low doses of deoxynivalenol applied per os on the presence of this mycotoxin in selected tissues of the alimentary canal of gilts. The study was performed on 39 animals divided into two groups (control, C; n = 21 and experimental, E; n = 18), of 20 kg body weight at the beginning of the experiment. Gilts received the toxin in doses of 12 µg/kg b.w./day (experimental group) or placebo (control group) over a period of 42 days. Three animals from two experimental groups were sacrificed on days 1, 7, 14, 21, 28, 35 and 42, excluding day 1 when only three control group animals were scarified. Tissues samples were prepared for high performance liquid chromatography (HPLC) analyses with the application of solid phase extraction (SPE). The results show that deoxynivalenol doses used in our study, even when applied for a short period, resulted in its presence in gastrointestinal tissues. The highest concentrations of deoxynivalenol reported in small intestine samples ranged from 7.2 (in the duodenum) to 18.6 ng/g (in the ileum) and in large intestine samples from 1.8 (in transverse the colon) to 23.0 ng/g (in the caecum). In liver tissues, the deoxynivalenol contents ranged from 6.7 to 8.8 ng/g.

Deoxynivalenol and oxidative stress indicators in winter wheat inoculated with Fusarium graminearum.

This study comprises analyses of contents of mycotoxins, such as deoxynivalenol and zearalenone, as well as the level of oxidative stress in ears of a susceptible wheat cultivar Hanseat and cv. Arina, resistant to a pathogenic fungus Fusarium graminearum. Starting from 48 h after inoculation, a marked increase was observed in the contents of these mycotoxins in ears of wheat; however, the greatest accumulation was recorded in the late period after inoculation, i.e., during development of disease. Up to 120 h after inoculation, in ears of both wheat cultivars, the level of deoxynivalenol was higher than that of zearalenone. The susceptible cultivar was characterized by a much greater accumulation of deoxynivalenol than the resistant cultivar. At the same time, in this cultivar, in the time from 0 to 72 h after inoculation, a marked post-infection increase was observed in the generation of the superoxide radical (O2•-). Additionally, its level, at all the time points after inoculation, was higher than in the control. In wheat cv. Arina, a markedly higher level of O2•- generation in relation to the control was found up to two hours after inoculation and, next, at a later time after inoculation. In turn, the level of semiquinone radicals detected by electron paramagnetic resonance (EPR) increased at later culture times, both in cv. Hanseat and Arina; however, in infested ears of wheat, it was generally lower than in the control. Analysis of disease symptoms revealed the presence of more extensive lesions in ears of a susceptible wheat cv. Hanseat than resistant cv. Arina. Additionally, ergosterol level as a fungal growth indicator was higher in ears of susceptible wheat than in the resistant cultivar.

Natural occurrence of fumonisins and ochratoxin A in some herbs and spices commercialized in Poland analyzed by UPLC-MS/MS method.

Unsanitary conditions during harvesting, drying, packing and storage stages in production and processing of spices and herbs could introduce mycotoxin contamination. The occurrence of ochratoxin A and fumonisins in popular spices and herbs was studied, using liquid chromatography-electrospray-mass spectrometry. Apart from mycotoxins, ergosterol as a factor indicating fungal development was also analysed. A total of 79 different samples commercialized in Poland were randomly purchased from popular markets were tested for mycotoxins. The frequency of samples with fumonisins was lower (31%) than ochratoxin A (49%). Free from mycotoxins were samples of bay leaf and white mustard. ERG content - in spice samples with high concentration level of mycotoxins - was also significantly higher than in samples with little to no mycotoxins.