Phenolic Amides Research Articles

Sensing performance of Schiff base-calix[4]arene including amide units for detection of pharmaceutically active compounds on QCM sensor system

This study aimed to investigate the sensing performance of a Quartz Crystal Microbalance (QCM) sensor coated with a calix[4]arene derivative (calixarene phenol amide, CPhA), containing both Schiff base and amide groups against various pharmaceutically active compounds (PhACs) such as ibuprofen, diphenhydramine, naproxen, and ascorbic acid in aqueous media. CPhA was successfully coated on the QCM crystal surface, and its surface properties were studied using Atomic Force Microscopy (AFM) and contact angle measurements. Sensing studies showed that the CPhA-coated QCM sensor detected more PhACs than the compound 4 (unfunctionalized derivative)-coated sensor. The highest frequency variation and binding ratio values were achieved with the QCM sensor with a relatively low coating amount. The CPhA-coated QCM sensor achieved higher adsorption capacity and was significantly more sensitive to all PhACs than the compound 4-coated one. The fabricated sensor showed remarkable reproducibility for all PhACs except naproxen (NAP). The fabricated sensor exhibited a remarkable sensing performance for detecting PhACs, which is promising for developing novel calix[4]arene-coated QCM sensors for PhACs.

Stereochemical insights into enantioselective antiplasmodial lignanamides from the twigs and leaves of Solanum erianthum

Stereochemical investigations on the twigs and leaves of Solanum erianthum afforded five pairs of lignanamide enantiomers and a previously undescribed phenolic amide (3). Particularly, two pairs of previously undescribed lignanamide racemates (1a/1b–2a/2b) represent the first case of natural products that feature an unreported 5/5-fused N/O-biheterocyclic core. Their structures, including the absolute configurations, were determined unambiguously by using spectroscopic analyses and electronic circular dichroism calculations. A speculative biogenetic pathway for 1–3 was proposed. Interestingly, these lignanamides exhibited enantioselective antiplasmodial activities against drug-sensitive Plasmodium falciparum 3D7 strain and chloroquine-resistant Plasmodium falciparum Dd2 strain, pointing out that chirality plays an important role in drug development.

Sustainable Chemical Derivatization of Hydroxycinnamic Acids

AbstractGreen solvents like ethyl acetate and acetone convert hydroxycinnamic acids into natural and unnatural derivatives such as amides, esters, and other valuable synthetic intermediates. Employing as protection‐activation a system based on an alkyl chloroformate and N‐methyl morpholine, ethyl acetate emerges as an excellent solvent for coupling O‐carbonate‐protected mixed anhydrides in acylation reactions of C‐protected amino acids, amines, and catalyzed acylation of alcohols. This results in high yields of O‐protected phenolic amides and esters. Acetone is preferred for acyl nucleophilic substitution reactions involving ionic species like free amino acids, sodium azide, and sodium hydroxide, all added in water. This approach releases the resultant O‐protected acylation products. Free phenolic compounds are promptly obtained on demand through carbonate deprotection. This synthetic method offers a simplified procedure and employs low‐cost reagents to prepare natural and unnatural hydroxycinnamic acid derivatives.

Comment on "Three New Dimers and Two Monomers of Phenolic Amides from the Fruits of Lycium barbarum and Their Antioxidant Activities".

This Comment critically addresses the article by Gao et al. (Gao, K., et al. J. Agric. Food Chem. 2015, 63, 1067-1075), providing the structural elucidation of three phenolamide dimers (neolignanamides) from the fruits of Lycium barbarum. A more recent article published by Chen et al. (Chen, H., et al. J. Agric. Food Chem. 2023, 71, 11080-11093) incorporates these structures into further research on the bioactivity of these compounds. Although the analytical techniques used by Gao et al. are adequate, in our opinion, the nuclear magnetic resonance (NMR) spectroscopic data have not been interpreted correctly, resulting in incorrect structures for three neolignanamides from the fruits of L. barbarum. In this Comment, an alternative interpretation of the NMR spectroscopic data and the corresponding structures are proposed. The proposed structures feature linkage types that are much more common for neolignanamides than the linkage types in the originally reported structures of these compounds.

Effect of pH, Amount of Metal Precursor, and Reduction Time on The Optical Properties and Size of Zinc Oxide Nanoparticles Synthesized Using Aqueous Extract of Rhizomes of Acorus calamus

Nanoparticles possess various unique characteristics compared to the corresponding bulk materials. Large band gap, non-toxic nature, and multi-applicability are the worthwhile characteristics of zinc oxide to be synthesized and studied. The size of nanoparticles can be controlled by varying the different experimental conditions. This paper reports the synthesis of zinc oxide nanoparticles by using an aqueous extract of rhizomes of Acorus calamus, where the bio-components present in aqueous extract acted as reducing agents. The size and band gap energy of zinc oxide nanoparticles were studied by varying different parameters such as pH, concentration of the metal precursor, and reduction time. The variations in the size of nanoparticles were studied by UV-visible spectroscopy. FTIR showed phenolic compounds, primary amines, and amides (proteins/enzymes) as the functional groups responsible for the reduction of metal precursors to form nanoparticles. The surface morphology of nanoparticles was studied by FE-SEM image. The FE-SEM image displayed the formation of various shapes and agglomeration of the nanoparticles. XRD pattern revealed that the average size of zinc nanoparticles is 10 nm. In vitro antibacterial activity of ZnO nanoparticles has been assayed against gram-positive and gram-negative bacteria. The growth inhibitory activity of nanoparticles against different bacterial pathogens has also been determined

Unlocking the potential of teak seed waste: carbonization for sustainable resource transformation

AbstractThe importance of carbonizing teak seed waste lies in unlocking its untapped potential for sustainable resource transformation while achieving waste management and converting the waste to more valuable products. This study investigates the production and characterization of teak‐seed biochar employing a top‐lit updraft reactor. The process parameters include a carbonization time of 2 h and a peak temperature of 379 °C, resulting in a substantial yield of 42%. Elemental analysis reveals the biochar's composition, consisting of 77.20% carbon and 18.79% potassium, positioning it as a valuable resource with versatile applications. The Fourier transform infrared (FTIR) analysis showcases a rich variety of functional groups within the biochar, including alcohols, carboxylic and phenolic groups, amides, and various hydrocarbon structures, signifying its multifaceted potential for applications like the adsorption of aqueous pollutants, soil stabilization, and enhanced ion‐exchange capacity. Textural assessments emphasize its noteworthy surface area (Brunauer, Emmett, and Teller (BET) analysis: 190.05 m2g−1; Langmuir: 1664.35 m2g−1), micropore volume (0.069 cm3g−1), and total pore volume (0.097 cm3/g−1), primarily characterized by mesoporous attributes (pore diameter: 2.153 nm), rendering it suitable for various applications. Scanning electron microscopy (SEM) analysis of surface morphology reveals a rough texture embellished with various‐sized and shaped particles, distinguished by their silvery, shiny appearance, which is attributed to the biochar's elemental composition, particularly the presence of potassium. These findings underline the promising potential of teak seed biochar across multiple applications, including agriculture, wastewater treatment, and environmental remediation.

Optimization of Ultrasound-Assisted Extraction and Characterization of the Phenolic Compounds in Rose Distillation Side Streams Using Spectrophotometric Assays and High-Throughput Analytical Techniques.

Lately, the essential oils industry has been one of the most expanding markets globally. However, the byproducts generated after the distillation of aromatic plants and their transformation to novel high-added value products consist of a major up-to-date challenge. Thus, the scope of the current study is the optimization of ultrasound-assisted extraction (UAE) for the recovery of phenolic compounds from rose (Rosa damascena) post-distillation side streams using Box-Behnken design. In particular, the highest total phenolic content (TPC) was achieved at 71% v/v ethanol-water solution, at 25 min, 40 mL/g dry sample and 53% ultrasound power, while ethanol content and extraction time were the most crucial factors (p-value ≤ 0.05) for UAE. Both solid (RSB) and liquid (LSB) rose side streams exhibited significant antiradical and antioxidant activities. The interpretation of attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectra confirmed the presence of compounds with properties such as phenolic compounds, phenolic amide derivatives, and alcohols in the extracts. Moreover, the flavonoids naringenin, quercetin, and kaempferol were the major phenolic compounds, identified in the extracts by liquid chromatography-tandem mass spectrometry analysis (LC-MS/MS), followed by gallic, protocatechuic, p-hydroxybenzoic, and rosmarinic acids. Furthermore, the LC-MS/MS results pinpointed the effect of factors other than the extraction conditions (harvesting parameters, climatic conditions, plant growth stage, etc.) on the phenolic fingerprint of RSB extracts. Therefore, RSB extracts emerge as a promising alternative antioxidant agent in food products.

Methyl 2-[3-(4-hydroxyphenyl)prop-2-enoylamino]-3-phenylpropanoate Is a Potent Cell-Permeable Anti-Cytokine Compound To Inhibit Inflammatory Cytokines in Monocyte/Macrophage-Like Cells.

Cytokines are signaling molecules involved in inflammation process. Interleukin (IL)-6 is one of pivotal inflammatory cytokines associated with many human diseases. Therefore, there are on-going efforts to find a therapeutic to inhibit IL-6 and other cytokines. Methyl 2-[3-(4-hydroxyphenyl)prop-2-enoylamino]-3-phenylpropanoate (MHPAP) is a phenolic amide ester, transported better than its non-ester form (NEF) in monocyte/macrophage-like cells. However, there is no information about the effects of their cell permeability on cytokines. Therefore, the effects of MHPAP and NEF on cytokines were investigated in lipopolysaccharide (LPS)-stimulated THP-1 and human peripheral blood mononuclear cells (PBMCs). In the THP-1 cells, MHPAP significantly inhibited IL-6, IL-1beta, IL-8, and tumor necrosis factor (TNF)-alpha (P < 0.05), but NEF showed no effects. MHPAP also inhibited nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) p65 phosphorylation in the THP-1 cells (P < 0.05), without significant effects on c-FOS, ATF-2, and JUN phosphorylations. Because NF-κB p65 is phosphorylated by IκB kinase (IKK), in silico analysis was performed on IKK. MHPAP was found to bind to IKK better than an IKK inhibitor ((E)-2-fluoro-4'-methoxystilbene). Furthermore, MHPAP inhibited the luminescence increased in the LPS-stimulated NF-κB-Luc2 THP-1 cells. As anticipated, MHPAP was also found to inhibit IL-6, IL-1beta, IL-8, and TNF-alpha significantly in LPS-stimulated PBMCs (P < 0.05). Especially, MHPAP inhibited IL-6 and IL-1beta with an IC50 of 0.85 and 0.87 µM, better than IL-8 (1.58 µM) and TNF-alpha (1.22 µM) in the cells. Altogether, the data suggest that cell permeability may have a significant impact on MHPAP's ability to inhibit cytokines and MHPAP may be used as a potent cell-permeable compound to inhibit inflammatory cytokines in monocyte/macrophage-like cells. SIGNIFICANCE STATEMENT: Potential effects of MHPAP and NEF on inflammatory cytokines (IL-6, IL-8, IL-1beta, and TNF-alpha) were investigated in LPS-stimulated THP-1 and PBMCs. Cell transport had a great impact on cytokine inhibition in the cells. MHPAP was also found to inhibit NF-κB pathway, which was supported by in silico and NF-κB reporter (Luc)-THP-1 data. Also, in LPS-stimulated PBMCs, MHPAP significantly inhibited IL-6, IL-1beta, IL-8, and TNF-alpha, suggesting that MHPAP may be a potent cell-permeable compound to inhibit inflammatory cytokines in monocyte/macrophage-like cells.

Unveiling the versatility of novel oxacalix[4]arene platform: Systematic screening and comparative study on biological and antioxidant potency

Calixarene, a third generation supramolecule, have made their signature in biomedical applications through their unique physicochemical characteristics. Oxacalixarene, a class of heteracalixarene, is less explored in this respect though it has manifested its potentiality in earlier very few reports. Here we are reporting for the first time a systematic and comparative study of biological activities of different oxacalix[4]arene(OC) systems. For this purpose, very common functional groups that are available in biomacromolecules like phenolic OH (DHOC), amine (DNOC), ester (DEOC) and amide (DAOC) have been considered for functionalization to basic OC platform and the newly synthesized compounds are characterized with state-of-the-art spectroscopic techniques. Analysis of DNA cleavage, DNA binding, cell cytotoxicity and antioxidant activity studies nicely define the diversity of OC in DNA protection or DNA damage phenomena. DHOC is able to protect oxidative cleavage of DNA up to 47 % against Fenton reagents. The order of binding constant (∼105) is observed in the following order: DHOC (phenolic OH) > DNOC (amine) > DAOC (amide). The article also reports the antioxidant activity of oxacalix[4]arene compounds for the first time, observed by DPPH inhibition assay. All the compounds possess antioxidant activities. Among those, DHOC shows maximum antioxidant activity, comparable to standard antioxidant ascorbic acid at 100 µM (DPPH: 60 µM). Indeed, the observed structure-function relationship of OC systems can be tailored in the future to design molecules that are specifically targeted for biomedical applications.

Identification and characterization of phenolamides in tea (Camellia sinensis) flowers using ultra-high-performance liquid chromatography/Q-Exactive orbitrap mass spectrometry.

Phenolamides (PAs) are important secondary metabolites present in plants with multiple bioactivities. This study aims to comprehensively identify and characterize PAs in tea (Camellia sinensis) flowers using ultra-high-performance liquid chromatography/Q-Exactive orbitrap mass spectrometry based on a lab-developed in-silico accurate-mass database. The PAs found in tea flowers were conjugates of Z/E-hydroxycinnamic acids (p-coumaric, caffeic and ferulic acids) with polyamines (putrescine, spermidine and agmatine). The positional and Z/E isomers were distinguished through characteristic MS2 fragmentation rules and chromatographic retention behavior summarized from some synthetic PAs. 21 types of PAs consisting of over 80 isomers were identified, and the majority of them were found in tea flowers for the first time. Among 12 tea flower varieties studied, they all possessed tris-(p-coumaroyl)-spermidine with the highest relative content, and C. sinensis 'Huangjinya' had the highest total relative contents of PAs. This study shows the richness and structural diversity of PAs in tea flowers.

Anti-osteoporosis bioactivity evaluation in zebrafish model of raw and salt-processed Achyranthes bidentata followed by liquid chromatography-mass spectrometry analysis and correlation analysis.

Achyranthes bidentata has been found to possess beneficial effects against osteoporosis, but there is still a lack of comprehensive studies on its anti-osteoporotic compounds. Therefore, in this study, we established a zebrafish osteoporosis model to evaluate the anti-osteoporotic effect of different fractions of raw and salt-processed A. bidentata. Among these fractions, the dichloromethane fraction showed the most promising anti-osteoporotic effect. To further investigate the active compounds responsible for the anti-osteoporosis effects, we prepared and analyzed the dichloromethane fraction of 10 batches of raw and salt-processed A. bidentata using liquid chromatography-mass spectrometry. As a result, we tentatively identified 19 compounds, including 11 saponins, three phenolic amides, three unsaturated fatty acids and two other compounds. To further narrow down the potential active compounds, we employed both orthogonal partial least squares discriminant analysis and gray relationship analysis. Through these analyses, we were able to identify eight compounds that showed a high correlation with the anti-osteoporosis effects of the dichloromethane fraction. Furthermore, we validated the anti-osteoporotic effects of β-ecdysterone, wogonin, ginsenoside Ro, oleanolic acid, linoleic acid and palmitic acid using the zebrafish model. These compounds demonstrated significant anti-osteoporotic effects, further supporting their potential as active compounds in A. bidentata.

Semi-synthesis of phenolic-amides and their cytotoxicity against THP-1, HeLa, HepG2 and MCF-7 cell lines

In the present study, we derivatized several hydroxycinnamic and hydroxybenzoic acids to phenolic amides (PAMs) via one step BOP mediated amide coupling reactions. Fifteen PAMs were synthesized in >40% yields and were screened for their cytotoxic activities against four cancer cell lines: THP-1 (leukaemia), HeLa (cervical), HepG2 (liver), and MCF-7 (breast), in comparison to 5-flurouracil (5-FU). Four amides showed IC50 ranging from 5 to 55 µM against all four cell lines. In contrast, tetradecyl-gallic-amide (13) affected only THP-1 leukaemia cells with IC50 of 3.08 µM. The activities of these compounds support the promise of phenolic amides as anticancer agents.

Structurally Diverse Phenolic Amides from the Fruits of Lycium barbarum with Potent α-Glucosidase, Dipeptidyl Peptidase-4 Inhibitory, and PPAR-γ Agonistic Activities.

A total of nine new phenolic amides (1-9), including four pairs of enantiomeric mixtures (3-5 and 8), along with ten known analogues (10-19) were identified from the fruits of Lycium barbarum using bioassay-guided chromatographic fractionation. Their structures were elucidated by comprehensive spectroscopic and spectrometric analyses, chiral HPLC analyses, and quantum NMR, and electronic circular dichroism calculations. Compounds 5-7 are the first example of feruloyl tyramine dimers fused through a cyclobutane ring. The activity results indicated that compounds 1, 11, and 13-17 exhibited remarkable inhibition against α-glucosidase with IC50 of 1.11-33.53 μM, 5-150 times stronger than acarbose (IC50 = 169.78 μM). Meanwhile, compounds 4a, 4b, 5a, 5b, 13, and 14 exerted moderate agonistic activities for peroxisome proliferator-activated receptor (PPAR-γ), with EC50 values of 10.09-44.26 μM. Especially,compound 14 also presented inhibitory activity on dipeptidyl peptidase-4 (DPPIV), with an IC50 value of 47.13 μM. Furthermore, the banding manner of compounds 14 and 17 with the active site of α-glucosidase, DPPIV, and PPAR-γ was explored by employing molecular docking analysis.

Poly(ester amide)s from biomass‐based 3,4‐dihydrocoumarine through Meldrum's acid mediated ketene chemistry

AbstractMeldrum's acid mediated ketene chemistry (MAMKC) is applied to synthesis of poly(ester amide)s in this work. An MA‐functionalized phenolic amide compound (MA_PhOH‐Am) is synthesized from the reaction between a MA‐functionalized amine and 3,4‐dihydrocoumarine (DHC, a biomass‐based chemical) through amine‐lactone addition reaction. Polymerization of MA_PhOH‐Am results in the corresponding poly(ester amide) (P(Es‐Am)), through MA thermolysis reaction (generating the corresponding ketene groups) and ketene‐phenol addition reaction. Both MA_PhOH‐Am and P(Es‐Am) have been characterized with spectral methods and thermal analysis. P(Es‐Am) has an inherent viscosity of 0.49 dL g−1, a molecular weight of 76,500 Da, a glass transition temperature of 145°C (tanδ peak in dynamic mechanical analysis), a thermal stability of about 320°C, and a storage modulus at 50°C of 1.0 GPa. In the stress–strain measurement, P(Es‐Am) exhibits a Young's modulus, a tensile strength, and an elongation at break of 10.6 ± 0.7 GPa, 165 ± 40 MPa, and 1.83 ± 0.41%, respectively. An effective approach for the synthesis of high‐performance poly(ester amide)s has been demonstrated.

Characterization of rice straw lignin phenolics and evaluation of their role in pollen tube growth in Cucurbita pepo L.

Rice straw lignin was extracted via alkaline hydrolysis and structurally characterized using FT-IR and 1H NMR spectra. Ethyl acetate extract of acid solubilized lignin was found to contain p-coumaric acid, ferulic acid and caffeic acid as major phenolic acids which were isolated and characterized using spectral data. Amides of isolated phenolic acids were synthesized by their reaction with propyl and butyl amines using microwave irradiation and analysed using spectral studies. Phenolic acids and amides were evaluated for their effect on pollen germination and tube growth in pumpkin. Pollen tube length was significantly increased with N-butyl-3-(3, 4-dihydroxyphenyl) acrylamide and N-butyl-3-(4-hydroxyphenyl) acrylamide at 5 ppm concentration than the control. These results could be utilised in increasing pollen tube length of Cucurbita pepo while making interspecific cross between C. moschata and C. pepo in order to transfer hull-less character of C. pepo to virus resistant C. moschata genotypes.

Two new phenolic amides from Allium chinense

ObjectiveTo isolate the phenolic amides from the dried bulbs of Allium chinense and investigate their myocardium protective activities. MethodsThe chemical constituents were isolated and purified by combining with silica gel column, Sephadex LH-20 column, HPLC and other chromatography techniques. Their structures were elucidated by NMR techniques and mass spectrometry. The isolated compounds were evaluated to determine their protective effect for myocardium cells in vitro. ResultsTwo new phenolic amides, namely, alichinemide I (1) and alichinemide II (2), and six konwn amides were isolated from the dried bulbs of A. chinense. The structures of compounds 3–8 were identified as 3-indolcarbaldehyde (3), 1-(2-aminophenyl)urea (4), 2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole-3-carboxylic acid (5), N-trans-feruloyltyramine (6), N-trans-p-coumaroyltyramine (7), and N-(3,4-dimethoxyphenethyl) acetamide (8). Compound 3 (50 μmol/L) showed significant inhibitory effect on the damage of H9c2 myocardial cells induced by H2O2in vitro. ConclusionCompounds 1 and 2 were new phenolic amides. Compound 3 could be one of the potential myocardium protective constituents of A. chinense.

Two New Nitrogen-Containing Glycosides From Stixis scandens

Phytochemical investigation of a methanol extract of Stixis scandens stems and leaves led to the isolation of 3 nitrogen-containing compounds (1-3) and 6 phenolics (4-9), which included 2 new glycosides, one a phenolic amide glucoside, scandemide (1), and the other an indole alkaloid glycoside, stixilenin (2). Their structures were elucidated by spectroscopic (1D- and 2D-NMR) and spectrometric (HR-ESI-MS) analyses, and acid hydrolysis. The isolated compounds were evaluated for their inhibitory effects on nitric oxide production in lipopolysaccharide-induced RAW264.7 cells.

Antibacterial activities of thirteen naturally occuring compounds from two Kenyan medicinal plants: Zanthoxylum paracanthum (Mildbr). Kokwaro (Rutaceae) and Dracaena usambarensis Engl. (Asparagaceae) against MDR phenotypes

• Root extract of Zanthoxylum paracanthum with good antibacterial activities. • Efflux pump inhibitor improved antimicrobial activities of Z. paracanthum extract. • All compounds exhibited activities on at least 2/13 bacteria tested. • Nitrogen-containing compounds showed the best activities against bacteria tested. • The phenolic amide, 1 was bactericidal against the standard and MDR isolates. The antibacterial potency of thirteen compounds reported from two distinct genera, Zanthoxylum (Rutaceae) and Dracaena (Asparagaceae) against a panel of sensitive and multi-drug resistant Gram-positive and Gram-negative bacteria is described. The minimal inhibitory concentrations (MICs) and minimal bactericidal concentrations (MBCs) determinations on the tested bacteria were established using modified rapid iodonitrotetrazolium chloride (INT) colorimetric assay. The root extract (50% MeOH/CH 2 Cl 2 ) of Zanthoxylum paracanthum was also combined with an efflux pump inhibitor, phenylalanine arginine β-naphthylamide (PAβN) (at 30 μg/mL), to evaluate the role of efflux pumps in the susceptibility of bacteria. Structure-Activity-Relationship (SAR) of related congeners is also described. The results of the MICs ranged from 4 (against Staphylococcus aureus ) to 16 μg/mL (towards Escherichia coli, Enterobacter aerogenes, Klebsiella pneumoniae, Providencia stuartii, Pseudomonas aeruginosa ) for Z. paracanthum extract and from 16 (against S. aureus MRSA3) to 1024 μg/mL (towards S. aureus ATCC25923 and MRSA3) for the compounds. Addition of phenylalanine arginine β-naphthylamide (PAβN) in the root extract of Z. paracanthum significantly increased the antibacterial potency of the extract against the tested bacteria, with the highest MICs values being observed at 1 μg/mL (against S. aureus and E. coli strains). The root extract of Z. paracanthum and most of the compounds exhibited an MIC/MBC ≤ 4 except for compound 1 , indicating their bactericidal status. Overall, this study provides baseline information on the antibacterial profiles of the studied samples against both Gram-positive and Gram-negative pathogenic bacteria. Structure modification of the moderately active compounds originating from Z. paracanthum and Dracaena usambarensis should be attempted in future studies towards the improvement of their antibacterial potencies.

Evaluation of chromatographic performance of three C18 columns for avenanthramides separation

Phenolic amides contained in oats (Avenanthramides; AVNs) are biologically active substances with strong antioxidant activity. In this paper, we evaluated efficiency of three C18 chromatographic columns (Symmetry, XBridge, Cortecs) with different particle technology and particle sizes for the separation of three major avenanthramides (AVN A, AVN B, AVN C). We compared columns in terms of retention times, retention factors of AVNs and in terms of other parameters such as number of theoretical plates, height equivalent to a theoretical plate, reduced plate height, resolution and in terms of peak symmetry, respectively. Limits of detection and limits of quantification of AVNs on all columns were calculated. Retention results of AVNs on individual columns showed a significant reduction in retention times of AVNs on solid core column with a particle size 2.7 μm compared to columns with particle size 3.5 μm. Within columns with 3.5 μm particles, separation on Symmetry C18 column appeared to be more efficient than on the XBridge C18 column. In general, results achieved on Cortecs C18 column can be considered as the best in terms of both separation efficiency and retention times.

Post-extrusion physical properties, techno-functionality and microbiota-modulating potential of hempseed (Cannabis sativa L.) hull fiber

One-third of hempseed is composed of fiber, yet this major nutrient is far understudied than the seed's oil, protein, polyphenol or cannabinoid fractions. Here we provided a comprehensive and novel study covering the monosaccharide-linkage composition, physical, functional and microbiota-shifting properties of the fiber-rich (>77%) hempseed hull, which is a major industrial processing by-product. Xylose and cellulose-derived 4-linked glucopyranosyl linkage residue dominated the monosaccharide profile and 1D/2D NMR molecular assignments of hempseed hull. Processing with extrusion technology altered the particle size distribution, FTIR structural characteristics, X-ray diffraction crystallinity and thermal stability of hempseed fiber. Extruded hempseed fiber showed significantly greater soluble fiber content, water and oil binding capacity, dynamic modulus and flow viscosity values in oil and oil-water dispersions, delayed starch gelatinization and inhibited its retrogradation. Integration of 16S rRNA gene sequencing and the rapidly emerging metaproteomics revealed a higher population of Megasphaera elsdenii and Lactobacillus spp., along with their expressed ferredoxin and enolases respectively, in porcine faecal samples after fermentation with hempseed hull fiber. Higher production of propionic, butyric and valeric acid from the microbiota was further observed in fiber-treated faecal inoculum. Finally, the possible microbiota modulating-effect of fiber-bounded unique phenylpropionamides ( N - trans -caffeoyltyramine and lignanamides) from hempseed hull was assessed for the first time. • The effects of extrusion on the fiber profile of hempseed hull were investigated. • Linkage and NMR analysis revealed the molecular composition of hempseed fiber. • Functionality of hempseed fiber was tested in oil, water and starch matrices. • Hempseed fiber may alter gut microbial populations and their expressed proteins. • Microbiota and phenolic amides interaction were explored.