Comparative Study of Different Column Types for the Separation of Polar Basic Hallucinogenic Alkaloids

The number of hallucinogenic compounds that have been separated simultaneously by liquid chromatography is limited. This research aimed to identify a column(s) that can allow for separation of several hallucinogens. The extent of separation of seven polar hallucinogenic tryptamine and phenethylamine derived alkaloids containing a basic N atom that becomes protonated at low pH values were investigated on five reverse-based columns and one hydrophilic interaction liquid chromatography (HILIC) column. An RP-phenyl and a negatively charged fused core HILIC were identified and recommended as effective columns in this regard. This research is the first to introduce a HILIC column in separation of…

Pholiotina cyanopus, a rare fungus producing psychoactive tryptamines

Abstract Pholiotina cyanopus was collected from wood chips and other woody remnants of undetermined tree species. Its basidiomata were found in June within the area of closed sawmill in the central part of Żywiec city (SW Poland). Description and illustration of Ph. cyanopus based on Polish specimens are provided and its ecology, general distribution and comparison with similar taxa – Pholiotina smithii, Pholiotina sulcatipes, and others are discussed as well. The identity of the active compounds of Ph. cyanopus was additionally determined. Liquid chromatography–mass spectrometry (LC-MS) data sets were obtained to support the occurrence of psilocybin and its analogues – psilocin, baeocystin…

Direct Analysis of Psilocin and Muscimol in Urine Samples Using Single Drop Microextraction Technique In-Line with Capillary Electrophoresis

The fully automated system of single drop microextraction coupled with capillary electrophoresis (SDME-CE) was developed for in-line preconcentration and determination of muscimol (MUS) and psilocin (PSC) from urine samples. Those two analytes are characteristic active metabolites of Amanita and Psilocybe mushrooms, evoking visual and auditory hallucinations. Study analytes were selectively extracted from the donor phase (urine samples, pH 4) into the organic phase (a drop of octanol layer), and re-extracted to the acidic acceptor (background electrolyte, BGE), consisting of 25 mM phosphate buffer (pH 3). The optimized conditions for the extraction procedure of a 200 &micro

The chemical composition of the floral extract of Epipogium Aphyllum sw. (Orchidaceae): A cluefor thier pollination biology

Epipogium aphyllum is a rare European obligate mycoheterotrophic orchid lacking chlorophyll. It has not been studied previously with respect to pollination biology. We studied the association between the composition of floral scent emission and its pollination systems. Field observation indicates that the main pollinators of Epipogium aphyllum are representatives of the genus Bombus (Hymenoptera), B. lucorum, B. hortorum, B. terrestris, B. pascuorum and B. proteus, and the genus Apis (Hymenoptera) namely A. mellifera. The main potential vector (observed to accidentally carry pollen), is most likely Episyrphus balteatus (Diptera, Syrphidae). The chemical composition of the floral extracts of…

Kinetics of photochemical isomerization of TFA-Gly-ZΔPhe into TFA-Gly-EΔPhe

The kinetics of photoisomerization of trifluoroacetyl-(Z)-dehydrophenylalanylglycine into trifluoroacetyl-(E)- dehydrophenylalanylglycine was studied in the hope that light-induced reaction could be useful as a means of preparation of the E-dehydropeptides. The obtained results indicate that if this reaction carried out under irradiation with light of wavelength 360 nm it is practically irreversible and gave nearly quantitatively pure Eisomer Significantly, expected cyclic side-products were not observed in the reaction mixture, thus proving the preparative potential of the elaborated procedure.

The Formation of Glycerol Oligomers with Two New Types of End Groups in the Presence of a Homogeneous Alkaline Catalyst

The purpose of this work was to synthesize and characterize oligoglycerols with the chains of more than four repeating units. Those oligoglycerols may have some interesting applications, among others, as polyoxyalkylation starters. The glycerol oligomerization process was carried out during 12 h, at 230 &deg

Oxidation of diclofenac in the presence of iron(II) octacarboxyphthalocyanine

Abstract This paper presents the results of the research on the influence of catalytic activity of iron(II) octacarboxyphthalocyanines (FePcOC) on the transformation of diclofenac (DCF) which is the most popular anti-inflammatory analgesic. Diclofenac poses a serious threat to the natural environment. The paper demonstrates that diclofenac, in the presence a monomeric form of iron octacarboxyphthalocyanine and hydroxyl radicals (HO•) (from H2O2), undergoes a transformation into diclofenac-2,5-iminoquinone (DCF-2,5-IQ), causing distinct changes in the UV–Vis absorption spectrum. In the presence of iron octacarboxyphthalocyanine and H2O2, the previously colourless diclofenac solution becomes …

The application of the supported liquid membrane and molecularly imprinted polymers as solid acceptor phase for selective extraction of biochanin A from urine

An efficient sample clean-up and preconcentration procedure for phytoestrogens analysis in urine has been developed. It was based on a combination of solid phase extraction with hollow-fiber supported liquid membrane and molecularly imprinted beads (MIPs-HF-SLM-SPE). The molecularly imprinted polymers (MIPs) were synthesized by precipitation polymerization technique with biochanin A (BCA) as a template, giving narrowly dispersed microspheres with a regular shape. As the functional monomer, (dimethylamino)ethyl methacrylate (-DEM) turned out to be better than methacrylic acid (MAA) to get the best-imprinted effects. The MIPs used as sorbents in the MIPs-HF-SLM-SPE extraction process exhibite…

Biocatalytic hydrogenation of the C=C bond in the enone unit of hydroxylated chalcones-process arising from cyanobacterial adaptations.

To verify the hypothesis that cyanobacteria naturally biosynthesising polyphenolic compounds possess an active enzymatic system that enables them to transform these substances, such an ability of the biocatalytic systems of whole cells of these biota was assessed for the first time. One halophilic strain and seven freshwater strains of cyanobacteria representing four of the five taxonomic orders of Cyanophyta were examined to determine the following: (i) whether they contain polyphenols, including flavonoids; (ii) the resistance of their cultures when suppressed by the presence of exogenous hydroxychalcones—precursors of flavonoid biosynthesis and (iii) whether these photoautotrophs can tra…

Determination of Glyphosate and AMPA in Food Samples Using Membrane Extraction Technique for Analytes Preconcentration

The method for determining glyphosate (NPG) and its metabolite AMPA (aminomethyl phosphonic acid) in solid food samples using UAE-SLM-HPLC–PDA technique was developed. Firstly, ultrasonic-assisted solvent extraction (UAE) and protein precipitation step were used for the analyte isolation. Then, the supernatant was evaporated to dryness and redissolved in distilled water (100 mL). The obtained solution was alkalized to pH 11 (with 1 M NaOH) and used directly as donor phase in SLM (supported liquid membrane) extraction. The SLM extraction was performed using 2 M NaCl (5 mL) as an acceptor phase. The flow rate of both phases (donor and acceptor) was set at 0.2 mL/min. The membrane extraction t…

Chemical Profiling of Polyfloral Belgian Honey: Ellagic Acid and Pinocembrin as Antioxidants and Chemical Markers

Chemical profiling of northern Belgian polyfloral honeys was performed to analyse their phenolic compound content (flavonoids and phenolic acids). First, samples were subjected to a standard analysis of their physicochemical properties, and then, the phenolic fraction was isolated and analysed using a HPLC/PAD method. All of the tested honeys showed a common and specific phenolic profile that could be the basis for the differentiation of polyfloral honeys of the Antwerp region from other polyfloral honeys. Chromatographic data indicated a high content of ellagic acid (9.13–13.66 mg/100 g honey), as well as the flavonoid pinocembrin (1.60–1.85 mg/100 g honey) in these honeys. Ellagic acid, a…

Transport mechanism of peptides through supported liquid membranes

Abstract The transport of selected dipeptides through supported liquid membranes impregnated with di(2-ethylhexyl) phosphoric acid in n-dihexylether has been investigated. The fluxes depend on the side chain of amino acids, presence in the peptide structure. The highest fluxes were obtained for the peptides extracted with the highest efficiency. It has been found that the hydrophobicity of investigated peptides, was not the major factor, influences their SLM permeation. In the conditions studied, it has been observed that the transport of peptide–carrier complex was depending on the acidic–basic properties of the analyte. The linearly least-square fittings of log {K1 + [H+]D} and log[(HR)2]…

An adventive Panaeolus antillarum in Poland (Basidiomycota, Agaricales) with notes on its taxonomy, geographical distribution, and ecology

Abstract Coprophilous fungus, Panaeolus antillarum rarely recorded in Europe, is reported here for the first time from the Augustow Plane, north-eastern Poland. This thermophilic species was found outdoors in August on horse dung mixed with straw. A chemical analysis did not confirm the presence of the psychoactive alkaloids in collected material. A complete description and illustration of the species based on Polish specimens are presented and notes on its taxonomy, ecology, world distribution and comparison with similar taxa — P. semiovatus var. semiovatus, P. semiovatus var. phalaenarum, and others are also provided.

Enantiodifferentiation of N-benzyloxycarbonylaminophosphonic and phosphinic acids and their esters using cyclodextrins by means of capillary electrophoresis

Capillary electrophoresis was successfully applied for separation of the enantiomers of N-benzyloxycarbonyl-alpha-aminophosphonic and alpha-aminophosphinic acids as well as their ethyl and phenyl monoesters with the use of a range of commercially available cyclodextrins (alpha, beta and hydroxypropyl-gamma-cyclodextrins) as chiral selectors. The dependence of effectiveness of separation on type and concentration of these chiral selectors as well as on pH of background electrolyte was examined in some detail.

Characterization of particle morphology of biochanin A molecularly imprinted polymers and their properties as a potential sorbent for solid-phase extraction

Abstract Molecularly imprinted polymers (MIPs) with biochanin A as a template were obtained using a bulk polymerization with non-covalent imprinting approach. The polymers were prepared in acetonitrile as porogen, using ethylene glycol dimethacrylate (EDMA) as cross-linking agent. The synthesis, with an application of 1′,1′-azobis(cyclohexanecarbonitrile) (ACHN) as an initiator, has been performed thermally. During the synthesis process the effect of different functional monomers such as methacrylic acid (MAA), acrylamide (AA) and 4-vinylpyridine (4-VP) was investigated. The application of nitrogen sorption porosimetry, scanning electron microscopy (SEM), and Fourier transform infrared spec…

Antioxidant Phenolic Compounds in Salvia officinalis L. and Salvia sclarea L.

Abstract The differences in the chemical composition of the phenolic compounds of Salvia officinalis versus Salvia sclarea growing in different habitats, were studied. First, the optimal solvent - methanol - for ultrasonic extraction of phenolic compounds from these plants was chosen experimentally. Total phenolic content and 1,1-diphenyl-2-picrylhydrazyl (DPPH) assays were determined spectrophotometrically. Total phenolic content was in the range of 63.9 to 134.4 mg GAE/g of plant depending on the studied species. The highest antiradical activity was displayed by the methanol fractions of S. sclarea varieties (83 and 67%). HPLC-DAD analysis of extracts was done in order to identify the pre…

Biocatalytic transformations of chalcones by cyanobacteria – HPLC–MS study

Application of Molecular Imprinted Polymers for Selective Solid Phase Extraction of Bisphenol A

Abstract Selective molecularly imprinted polymers (MIPs) with bisphenol A as template were synthesized using the non-covalent imprinting approach. MIPs were prepared using thermally initiated polymerization with 1,1’-azobis(cyclohexanecarbonitryle) (ACHN) as initiator and ethylene glycol dimethacrylate (EDMA) as a cross-linking agent. The tested functional monomers included methacrylic acid, acrylamide, and 4-vinylpyridine. The selectivity of the BPA-MIP for the solid phase extraction of bisphenol A was tested in samples containing other related alkylphenols. The polymers prepared in acetonitrile using methacrylic acid or acrylamide as monomer showed the highest selectivity towards target a…

’Structural constraints in cyanobacteria-mediated whole-cell biotransformation of methoxylated and methylated derivatives of 2′-hydroxychalcone

Halophilic and freshwater strains of cyanobacteria representing the Oscillatoriales, Nostocales, Chroococcales, and Synechococcales orders of Cyanophyta were examined to determine (i) the resistance of their cultures when suppressed by the presence of exogenous methoxylated and methylated derivatives of 2'-hydroxychalcone, (ii) morphological changes in cells treated with the tested chalcones and, most importantly, (iii) whether these photoautotrophic microorganisms transform chalcone derivatives in a structure- or strain-dependent manner. The growth of cyanobacterial cultures depended on chalcone derivatives and the strain; nevertheless, trends for correlations between these parameters are …

Titanium and vanadium catalysts with oxazoline ligands for ethylene-norbornene (co)polymerization

A series of catalysts, (Py-ox)TiCl4, (Py-box)TiCl4, (Py-ox)VCl3, (Py-box)VCl3, SIL/(Py-ox)VCl3, SIL/(Py-box)VCl3, with 2-(1,3-oxazolin-2-yl)pyridine (Py-ox) and 2,6-bis(1,3-oxazolin-2-yl)pyridine (Py-box) ligands, silica support modified by 1-[3-(triethoxysilyl)propyl]pyridinium ethylchloroaluminate ionic liquid (SIL), activated by AlEt2Cl, AlEtCl2, and methylaluminoxane (MMAO) were studied in ethylene polymerization and ethylene-norbornene copolymerization. Single-crystal X-ray diffraction is given for both Py-ox and Py-box. The complexation was confirmed by NMR and ESI-MS methods. All complexes were found to be active in ethylene polymerization with better performance of the vanadium cata…

Secondary metabolites from the aerial parts of Cytisus villosus Pourr

Phytochemical investigation of the aerial parts of Cytisus villosus Pourr. resulted in the isolation and characterization of a new isoflavan, (3S, 4S)-2′,4′-dihydroxy-3′-methoxy-6,7-methylenedioxyisoflavan- 4-ol (1), and a new monoterpene, (4R,6S)-4-hydroxy-2,2,6-trimethyl-9-oxabicyclo [4.2.1] non-1(8)-en-7-one (2), together with four known flavonoids: geinstein (3), chrysin (4), chrysin -7-O-β-D-glucopyranoside (5) and 2″-O-α-L-rhamnosylorientin (6). The structures of the new compounds were elucidated on the basis of extensive spectroscopic analysis, including 1D, 2D NMR ((1)H, (13)C, COSY, TOCSY, HMBC and HSQC) and HRESIMS. The absolute configurations of 1 and 2 were established by the co…

Determination of muscimol and ibotenic acid in mushrooms of Amanitaceae by capillary electrophoresis

In this study, the CZE method for rapid quantitative and qualitative determination of ibotenic acid and muscimol in Amanita mushrooms naturally grown in Poland was developed. The investigations included the species of A. muscaria, A. pantherina, and A. citrina, collected in southern region of Poland. The studied hallucinogenic compounds were effectively extracted with a mixture of methanol and 1 mM sodium phosphate buffer at pH 3 (1:1 v/v) using ultrasound-assisted procedure. The obtained extracts were separated and determined by CZE utilizing a 25 mM sodium phosphate running buffer adjusted to pH 3 with 5% content of acetonitrile v/v. The calibration curves for both analytes were linear in…

Supported liquid membrane extraction with single hollow fiber for the analysis of fluoroquinolones from environmental surface water samples

Abstract In this work, the simple analytical method for the determination of four fluoroquinolone antibiotics: ciprofloxacin, enrofloxacin, norfloxacin and danofloxacin, in environmental surface water samples is described. Sample pretreatment step was performed by the application of a technique based on supported liquid membrane extraction with the configuration of single hollow fiber (HF-SLM). The HPLC system with diode array detection was used for final analysis of studied analytes. Various parameters affecting the extraction efficiency during HF-SLM enrichment, such as type of membrane diluent, pH of donor (sample) and acceptor phases, as well as an enrichment time and salt content of sa…

Do differences in chemical composition of stem and cap of Amanita muscaria fruiting bodies correlate with topsoil type?

Fly agaric (Amanita muscaria) was investigated using a 1H NMR-based metabolomics approach. The caps and stems were studied separately, revealing different metabolic compositions. Additionally, multivariate data analyses of the fungal basidiomata and the type of soil were performed. Compared to the stems, A. muscaria caps exhibited higher concentrations of isoleucine, leucine, valine, alanine, aspartate, asparagine, threonine, lipids (mainly free fatty acids), choline, glycerophosphocholine (GPC), acetate, adenosine, uridine, 4-aminobutyrate, 6-hydroxynicotinate, quinolinate, UDP-carbohydrate and glycerol. Conversely, they exhibited lower concentrations of formate, fumarate, trehalose, α- an…

Hybrid TiO2 @ phthalocyanine catalysts in photooxidation of 4-nitrophenol: Effect of the matrix and sensitizer type

Abstract Microcrystalline and nanocrystalline anatase (TiO2) based hybrid photocatalysts including selected phthalocyanine sensitizers were explored in photooxidation of 4-nitrophenol (4-NP) in water. Composites obtained with the homemade pure nano-anatase displayed a very poor catalytic performance compared to the other ones prepared from the commercial Tioxide-Huntsman (micro) and Evonik P25 (nano) products. In particular, the microcrystalline anatase impregnated with sandwich phthalocyanines of Gd or Yb showed excellent results both in photooxidation of 4-NP and hydroquinone, and proved the only ones which completely removed these two compounds from the system during the same reaction cy…

2-(1,3-Oxazolin-2-yl)pyridine and 2,6-bis(1,3-oxazolin-2-yl) pyridine

The data presented in this article are related to research articles “Titanium and vanadium catalysts with oxazoline ligands for ethylene-norbornene (co)polymerization (Ochędzan-Siodłak et al., 2018). For the title compounds, 2-(1,3-oxazolin-2-yl)pyridine (Py-ox) and 2,6-bis(1,3-oxazolin-2-yl)pyridine (Py-box), the single-crystal X-ray diffraction measurement together with NMR, GC, MS, DSC analysis, like also the method of crystallization are presented. Keywords: Ligands, Oxazoline, Pyridine, Conformation, Association

Research on Acute Toxicity and the Behavioral Effects of Methanolic Extract from Psilocybin Mushrooms and Psilocin in Mice

The pharmacological activities and acute toxicity of the psilocin (PC) and dried residues of the crude extracts of psychotropic mushrooms were investigated in mice. The hallucinogenic substances were effectively isolated, by using methanol, from the species of Psilocybe semilanceata and Pholiotina cyanopus, that were collected in the north-east region of Poland. The chemical analysis of these extracts, which was performed by liquid chromatography with mass spectrometry detection (LC-MS), indicated the presence of psilocin and other hallucinogenic substances, including indolealkylamines and their phosphorylated analogues. When the pure psilocin or fungal extracts were used, slight difference…

Surface molecularly imprinted silica for selective solid-phase extraction of biochanin A, daidzein and genistein from urine samples

Selective molecularly imprinted silica polymer (SiO2MIP) for extraction of biochanin A, daidzein and genistein was synthesized using the surface molecular imprinting technique with the silica gel as a support. Biochanin A (BCA) was used as a template, 3-aminopropyltriethoxysilane (APTES) as a functional monomer, and tetraethoxysilicane (TEOS) as a cross-linker. Non-imprinted polymer with the sol–gel process (SiO2NIP) was also prepared for comparison. The synthesized polymers were characterized by Fourier transform infrared spectrometry (FTIR), scanning electron microscopy (SEM) and a standard Brunauer-Emett-Teller (BET) and Barret–Joyner–Halenda (BJH) analysis. The obtained results indicate…

Sample pretreatment techniques for oligopeptide analysis from natural sources

The analysis of oligopeptides in samples of food, tissues, and body fluids attracts considerable attention. The complexity of such samples requires efficient sample preparation (i.e., concentration and cleanup) procedures to remove interfering endogenous compounds and inorganic or organic salts. The methods of sample pretreatment that enable effective and selective isolation and/or preconcentration of oligopeptides from complex sample matrices have been reviewed. In each case, examples of application were presented and discussed, taking into account selectivity, enrichment, method automation, cleanup, and environmental aspects of the developed methods.

Characterization of hydrocarbon-degrading and biosurfactant-producing Pseudomonas sp. P-1 strain as a potential tool for bioremediation of petroleum-contaminated soil

The Pseudomonas sp. P-1 strain, isolated from heavily petroleum hydrocarbon-contaminated soil, was investigated for its capability to degrade hydrocarbons and produce a biosurfactant. The strain degraded crude oil, fractions A5 and P3 of crude oil, and hexadecane (27, 39, 27 and 13 % of hydrocarbons added to culture medium were degraded, respectively) but had no ability to degrade phenanthrene. Additionally, the presence of gene-encoding enzymes responsible for the degradation of alkanes and naphthalene in the genome of the P-1 strain was reported. Positive results of blood agar and methylene blue agar tests, as well as the presence of gene rhl, involved in the biosynthesis of rhamnolipid, …

Bioactive Alkaloids of Hallucinogenic Mushrooms

Abstract The aim of our chapter is to review recent developments in a group of medicinally important natural products–alkaloids, with reference to the structure–activity studies in respect of certain diseases. Alkaloids covered by our review come from mushrooms called “hallucinogenic.” Hallucinogenic compounds have been chemically identified in mushrooms belonging to various genera, e.g., Agrocybe, Amanita, Conocybe, Galerina, Gymnopilus, Hypholoma, Inocybe, Panaeolus, Psilocybe, Pholiotina, Pluteus, and Weraroa [J.W. Allen, Ethnomycol. J. Sacred Mushroom Stud. 9 (2012) 130–175]. One of the largest classes of alkaloids is indole alkaloids. Indoles are probably the most widely distributed he…

Multivariate optimization of the hollow fibre liquid phase microextraction of muscimol in human urine samples.

Abstract A liquid phase microextraction based on hollow fibre followed by liquid chromatographic determination was developed for the extraction and quantitation of the hallucinogenic muscimol from urine samples. Method applicability on polar hallucinogens was also tested on two alkaloids, a psychedelic hallucinogen, tryptamine and a polar amino acid, tryptophan which exists in its charged state in the entire pH range. A multivariate design of experiments was used in which a half fractional factorial approach was applied to screen six factors (donor phase pH, acceptor phase HCl concentration, carrier composition, stirring rate, extraction time and salt content) for their extent of vitality i…

Phenolic compounds and abscisic acid as potential markers for the floral origin of two Polish unifloral honeys

The phenolic profiles of Polish honey samples from heather (Calluna vulgaris L.) and buckwheat (Fagopyrum esculentum L.) were determined. The phenolic components were isolated from honey samples using Amberlite-XAD-2 as a solid-phase extraction sorbent. For the determination of the composition of the honey extracts HPLC with photodiode array detector was applied. Identification and quantification of phenolics was performed by comparison of their retention times and UV spectra with those of standard solutions of pure reference substances and by using those references as external standards. From among 20 commercially available standards over 15 of them were identified as present in all analys…

CCDC 1815355: Experimental Crystal Structure Determination

Related Article: Wioletta Ochędzan-Siodłak, Anna Bihun-Kisiel, Dawid Siodłak, Anna Poliwoda, Błażej Dziuk|2018|Data in Brief|21|449|doi:10.1016/j.dib.2018.09.129

CCDC 1580983: Experimental Crystal Structure Determination

Related Article: Wioletta Ochędzan-Siodłak, Anna Bihun-Kisiel, Dawid Siodłak, Anna Poliwoda, Błażej Dziuk|2018|Data in Brief|21|449|doi:10.1016/j.dib.2018.09.129