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      An innovative monolithic zwitterionic stationary phase for the separation of phenolic acids in coffee bean extracts by capillary electrochromatography

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          Abstract

          A methacrylate based monolith, containing the innovative zwitterionic monomer (3-allyl-1-imidazol) propane sulfonate, was prepared in 100 µm I.D. silica capillaries by UV initiated photo-polymerization. Composition of the porogen, i.e. a mixture of 1-propanol, 1,4 butanediol and water, was of great importance to obtain a homogeneous monolith with satisfactory permeability and good electrochromatographic performance. Morphology of the stationary phase was studied in Scanning Electron Microscopy and IR experiments, which revealed a good attachment to the capillary wall, flowthrough-pores in the range of 0.5–2 µm, and a continuous monolithic structure. The developed material was well suited for the analysis of six common phenolic acids (salicylic, cinnamic, syringic, rosmarinic, caffeic and chlorogenic acid) by CEC. Their separation was possible in less than 8 min with a mobile phase comprising a 12 mM aqueous ammonium acetate solution with pH 8.5 and acetonitrile, at an applied voltage of - 20 kV. The developed method was validated (R 2 ≥ 0.995; LOD ≤ 3.9 µg mL −1, except for salicylic acid; recovery rates from 94 to 104%) and successfully used for the determination of phenolic acids in Coffea arabica samples. All of them contained cinnamic, syringic and caffeic acid, however only in unroasted coffee beans chlorogenic acid (0.06%) was found. The quantitative results were in good agreement to reported literature data.

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          Determination of free and total phenolic acids in plant-derived foods by HPLC with diode-array detection.

          A high-performance liquid chromatographic (HPLC) method with diode-array detection (DAD) was used to identify and quantify free and total phenolic acids (m-hydroxybenzoic acid, p-hydroxybenzoic acid, protocatechuic acid, gallic acid, vanillic acid, syringic acid, o-coumaric acid, m-coumaric acid, p-coumaric acid, caffeic acid, ferulic acid, sinapic acid, chlorogenic acid, and ellagic acid) in plant foods. Free phenolic acids were extracted with a mixture of methanol and 10% acetic acid. Bound phenolic acids were liberated using first alkaline and then acid hydrolysis followed by extraction with diethyl ether/ethyl acetate (1:1). All fractions were quantified separately by HPLC. After HPLC quantification, results of alkali and acid hydrolysates were calculated to represent total phenolic acids. Ellagic acid was quantified separately after long (20 h) acid hydrolysis. The methods developed were effective for the determination of phenolic acids in plant foods. DAD response was linear for all phenolic acids within the ranges evaluated, with correlation coefficients exceeding 0.999. Coefficients of variation for 4-8 sample replicates were consistently below 10%. Recovery tests of phenolic acids were performed for every hydrolysis condition using several samples. Recoveries were generally good (mean >90%) with the exceptions of gallic acid and, in some cases, caffeic acid samples.
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            Chlorogenic acid compounds from coffee are differentially absorbed and metabolized in humans.

            Chlorogenic acids (CGA) are abundant phenolic compounds in coffee, with caffeoylquinic (CQA), feruloylquinic (FQA), and dicaffeoylquinic (diCQA) acids being the major subclasses. Despite the potential biopharmacological properties attributed to these compounds, little is known about their bioavailability in humans. In this study, we evaluated the distribution profile of the major CGA isomers and metabolites in plasma and urine of 6 healthy adults for 4 h after brewed coffee consumption. Three CQA isomers and 3 diCQA isomers were identified in the plasma of all subjects after coffee consumption, whereas 2 FQA were identified in only 1 subject. Two plasma concentration peaks were observed, the first at 0.5-1.0 h and the second at 1.5-4.0 h after coffee consumption. The molar ratio CQA:diCQA was 12.2 in the brewed coffee, whereas in plasma it ranged from 0.6-2.9. The molar ratios 5-CQA:3-CQA and 5-CQA:4-CQA were consistently higher in plasma than in the brew. The main CGA metabolites identified in urine after coffee consumption were: dihydrocaffeic, gallic, isoferulic, ferulic, vanillic, caffeic, 5-CQA, sinapic, rho-hydroxybenzoic, and rho-coumaric acids (gallic and dihydrocaffeic acids being the major ones). This study indicates that the major CGA compounds present in coffee are differentially absorbed and/or metabolized in humans, with a large inter-individual variation. Moreover, urine does not appear to be a major excretion pathway of intact CGA compounds in humans.
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              Characterization of phenolic compounds in different anatomical pear ( Pyrus communis L.) parts by ultra-performance liquid chromatography photodiode detector-quadrupole/time of flight-mass spectrometry (UPLC-PDA-Q/TOF-MS)

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                Author and article information

                Journal
                0370534
                520
                Anal Chim Acta
                Anal. Chim. Acta
                Analytica chimica acta
                0003-2670
                1873-4324
                7 April 2017
                02 February 2017
                22 April 2017
                22 April 2017
                : 963
                : 136-142
                Affiliations
                [a ]Institute of Pharmacy, Pharmacognosy, University of Innsbruck, Innsbruck, Austria
                [b ]Institute for Analytical Chemistry and Radiochemistry, University of Innsbruck, Innsbruck, Austria
                [c ]Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Austria
                Author notes
                [* ] Corresponding author. Institute of Pharmacy, Pharmacognosy, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria. Markus.Ganzera@ 123456uibk.ac.at (M. Ganzera).
                Article
                EMS72231
                10.1016/j.aca.2017.01.048
                5388181
                28335967
                44ac2e6b-c2e0-4c44-b00d-f6716292dafd

                This is an open access article under the CC BY license ( http://creativecommons.org/licenses/by/4.0/).

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                Categories
                Article

                Analytical chemistry
                cec,zwitterionic stationary phase,natural products,coffee
                Analytical chemistry
                cec, zwitterionic stationary phase, natural products, coffee

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