DOCSLIB.ORG

Chlorogenic Acid Biosynthesis: Characterization of a Light-Induced

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Chlorogenic Acid Biosynthesis: Characterization of a Light-Induced ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS Vol. 258, No. 1, October, pp. 226-232, 1987 Chlorogenic Acid Biosynthesis: Characterization of a Light-Induced Microsomal 5O-(4-Coumaroyl)-D-quinate/shikimate 3’-Hydroxylase from Carrot (Daucus carota L.) Cell Suspension Cultures’ THOMAS KijHNL, ULRICH KOCH, WERNER HELLER, AND ECKARD WELLMANN Biologisches Institut II der Universitti Fm&wg, Schiinzlestrasse I, D-7800 Frea’burg, Federal Republic of Germany Received March 19,1987, and in revised form June 16,1987 Microsomal preparations from carrot (Daucus carota L.) cell suspension cultures cat- alyze the formation of tram-50-caffeoyl-D-quinate (chlorogenate) from trans-5-O-(4- coumaroyl)-D-quinate. trans-5-0-(4-Coumaroyl)shikimate is converted to about the same extent to trans-5Gcaffeoylshikimate. trans-4-0-(4-Coumaroyl)-D-quinate, tram-3-0-(4- coumaroyl)-D-quinate, trane-lcoumarate, and c&Z-5-0-(4-coumaroyl)-D-quinate do not act as substrates. The reaction is strictly dependent on molecular oxygen and on NADPH as reducing cofactor. NADH and ascorbic acid cannot substitute for NADPH. Cytochrome c, Tetcyclacis, and carbon monoxide inhibit the reaction suggesting a cytochrome P- 450-dependent mixed-function monooxygenase. Competition experiments as well as in- duction and inhibition phenomena indicate that there is only one enzyme species which is responsible for the hydroxylation of the 5-0-(4-coumaric) esters of both D-quinate and shikimate. The activity of this enzyme is greatly increased by in V&JOirradiation of the cells with blue/uv light. We conclude that the biosynthesis of the predominant caffeic acid conjugates in carrot cells occurs via the corresponding I-coumaric acid esters. Thus, in this system, 5-O-(4-coumaroyl)-D-quinate can be seen as the final intermediate in the chlorogenic acid pathway. 8 1987Academic press. I~C. Chlorogenic acid, 5-0-caffeoyl-D-quinic zymatic studies have shown that the es- acid, is one of the most widespread hy- terification of D-quinate requires hydrox- droxycinnamic acid derivatives known in ycinnamic acids activated by conjugation the plant kingdom (1). Various physiolog- with /3-D-glucose or coenzyme A. Kojima ical roles have been suggested for this and Villegas recently reported on the con- compound. These include growth regula- version of 4-~COUmarOyl-D-glUCOSe (2) and tion and disease resistance ((1) and liter- caffeoyl-D-glucose (3) to the corresponding ature cited therein). 5-O-esters of D-quinate by an enzyme Numerous reports on the biosynthesis of preparation from sweet potato. These re- chlorogenic acid have been published. En- actions have not yet been described for other plant systems. Transesterification ’ This work was supported by Deutsche For- via hydroxycinnamoyl-CoA esters me- schungsgemeinschaft (We 567/5-l). diated by hydroxycinnamoyl-CoA:D-quin- * Present address: Gesellschaft ftir Strahlen und ate hydroxycinnamoyl transferase (CQT),4 Umweltforschung Mtinchen, Ingolst&dter Landstrasse 1, D-8042 Neuherberg, FRG. ’ Abbreviations used: CQT, hydroxycinnamoyi- 3 To whom correspondence should he addressed at CoA:D-quinate hydroxycinnamoyl transferase; CST, Lehrstuhl fur Botanik, Biologisches Institut II der hydroxycinnamoyl-CoAshikimate hydroxycinnamoyl IJniversit%t, Schlnzlestraase 1, D-7800 Freihurg, FRG. transferase. 0003-9861/87 $3.00 226 Copyright 0 1987 by Academic Press, Inc. All rights of reproduction in any form reserved. Daucus carom 5-@(4-COUMAROYL)-D-QUINATE/SHIKIMATE 3’-HYDROXYLASE 227 on the other hand, has been demonstrated HO-..? OOH in a wide range of plants (4). In some cases, CQT activity is increased in response to HCf$OhoH external stimuli, such as light (5-7) or low temperature (8). This increase in enzyme activity is accompanied by accumulation of HO... COOH chlorogenic acid in the tissue. NADPH CQT exhibits high specificity for the ac- ceptor D-quinate. The relative specificities - 02 wQoJ-Q(,~ for the CoA esters differ from one plant system to the other, 4-coumaroyl-CoA and FIG. 1. Hydroxylation of trons-5-0-(4-coumaroyl)- caffeoyl-CoA being almost always the only D-quinate to trans-5-0-caffeoyl-n-quinate (chloro- substrates (4). The question remains as to genate). at which level the 3-hydroxylation of the 4-coumaroyl moiety occurs in vivo. MATERIALS AND METHODS The hydroxylation of both free 4-cou- marate (9, 10) and 4-coumaroyl-D-quinate Materials. Chlorogenic acid was purchased from Roth (Karlsruhe). Methanol-d, and trimethylsilane (11) has been reported to be catalyzed by were from EGA-Chemie (Weinheim). Cytochrome P- phenolases. These enzymes have, however, 450 specific inhibitors were kindly provided by Pro- not been proved to be specifically involved fessor H. Grisebach, Freiburg. All other chemicals in chlorogenic acid biosynthesis. and enzymes were obtained or prepared as described Recent investigations on elicitor-induced previously (12). parsley (Petroselinum crispurn Miller) cell Cell cultures. Carrot (Daucus curotu) cell suspension suspension cultures have shown that hy- cultures were a kind gift from Dr. U. Matern, Freiburg. droxylation of 5-0-(4-coumaroyl)shikimate The cells were grown in B-5 medium (16) at 25°C in can be mediated by a microsomal cyto- the dark. Two and one half to three grams of 7-day- chrome P-450-dependent mixed-function old cultures was propagated in 40 ml of fresh medium. Light induction Seven-day-old cells were washed monooxygenase (12). A hydroxycinnamoyl- with fresh medium and an inoculum of 10 g was CoA:shikimate hydroxycinnamoyl trans- transferred to 40 ml medium. After 10 to 12 h in the ferase (CST) is induced concomitantly. This dark, the cells were irradiated for 20 h with Osram L suggests the possibility of a flux of 4-cou- 40 W/73 fluorescent tubes (A,,,,, 350 nm, half band- marate into the ester pathway, at which width 40 nm, 7.8 W m-a) (1’7). stage 3-hydroxylation of the coumaroyl Chromatography. TLC on cellulose plates (Merck, moiety occurs. In the case of chlorogenic Darmstadt) was performed with 2% formic acid (I). acid biosynthesis, a similar pathway for 4- HPLC was carried out on a lo-pm Lichrosorb RP-18 coumaroyl 3-hydroxylation might be ex- column (0.5 X 25 cm) (Merck, Darmstadt) using water/ pected, since some earlier tracer studies acetonitrile/acetic acid (87/12/l, v/v/v) (II) and (84/ 15/l, v/v/v) (III) as solvents. have shown 5-o-(4-coumaroyl)-D-quinate Enzymatic preparation of 5-0-(&coumaroyl)-D- to be an intermediate (13,14). PiniC acid. Preparation of 5-@(4-coumaroyl)-D-quinic Carrot (Duucus carob L.) cell cultures acid was carried out according to (12) using 300 nmol are known to produce chlorogenic acid (15). I-coumaroyl-CoA and 1 rmol D-quinate in a volume We have recently found that the formation of 500 ~1. The product was extracted twice with 250 of this compound can be increased by ir- /.d of l-butanol and evaporated to dryness. After TLC, radiation with blue/uv light. the product was purified further by HPLC with solvent In this paper, we report on a particulate III. The product was identified by ‘H NMR spectros- hydroxylase from carrot cell suspension copy in methanol-d4. The data were compared with cultures responsible for the conversion of those obtained from chlorogenic acid. 5-O-(4-coumaroyl)-D-quinate to chloro- 5-@Caffeoyl-D-quinate: 7.56 (d, H-0, 15.9), 7.04 (d, H-2’, ZO),6.95 (dd, H-6,2.0/8.2), 6.77 (d, H-5,8.2), 6.26 genate (Fig. l), which is induced by blue/ (d, H-a, 15.9), 5.34 (m, H-5,4.3/9.7/9.7), 4.17 (m, H-3, uv light. The relationship between the 4- 5.0/3.3/3.3), 3.72 (dd, H-4,3.2/8.6), 2.24 (m, H&q, 2.1/ coumaroyl3-hydroxylases from carrot and 4.5/13.4), 2.17 (dd, H-Zax, 3.3/14.1), 2.07 (dd, H-Gax, parsley cells is discussed. 9.7/13.3), 2.06 (m, H-Zeq, 2.1/5.0/14.1); (cf. (18)). 228 KUHNL ET AL. 5-0-(4-Coumaroyl)-D-quinate: 7.63 (d, H-8, 15.8), (1.7 TBq/mol). In the presence of an excess of micro- 7.42 (d, H-Z/H-6’, 6.5), 6.76 (d, H-3’/H-5’, ‘7.2), 6.33 (d, somal protein, cinnamate I-hydroxylase yielded up to H-a, 14.9), 5.40 (H-5), 4.24 (H-3), 3.74 (H-4). 1.5 nmol4-[3-‘%]coumarate in the assay. Preparation of enzymes. Crude extracts and micro- Product ident@ztion Chlorogenate prepared by somal fractions were prepared from freshly harvested enzymatic hydroxylation of 5-o-(d-COUUXirOyl)-D- carrot cells as described earlier (12), but with 0.1 M quinate was identified by TLC (solvent I) and HPLC potassium phosphate buffer, pH 7.5, with 1.5 IUM di- (solvent II). thioerythritol and 10% (w/v) sucrose. The microsomal Assaysfor other enzymes. CQT was measured spec- preparations were frozen in liquid nitrogen and stored trophotometrically as described by Ulbrich and Zenk at -70°C. (4). Cinnamate 4-hydroxylase was measured as de- Synthesis of hydrvxycinnamoyl-D-quinic acids. (a) scribed previously (12). The 3-O and 4-O isomers of I-coumaroyl- and caffeoyl- Other analytical methods. Protein was determined D-quinic acids were prepared according to the method by a modified Lowry procedure (12). ‘H NMR spectra of Hanson (19) by keeping a neutral solution of 5-O were recorded on a Bruker WM 300 spectrometer. (I-coumaroyl) quinic acid and chlorogenic acid, re- spectively, at 90°C for 30 min. The products were ex- RESULTS AND DISCUSSION tracted with I-butanol.
Load more

Recommended publications
  • Isolation and Functional Characterization of a Cdna Coding A
    Isolation and functional characterization of a cDNA coding a hydroxycinnamoyltransferase involved in phenylpropanoid biosynthesis in Cynara cardunculus L Cinzia Comino, Sergio Lanteri, Ezio Portis, Alberto Acquadro, Annalisa Romani, Alain Hehn, Romain Larbat, Frédéric Bourgaud To cite this version: Cinzia Comino, Sergio Lanteri, Ezio Portis, Alberto Acquadro, Annalisa Romani, et al.. Isolation and functional characterization of a cDNA coding a hydroxycinnamoyltransferase involved in phenyl- propanoid biosynthesis in Cynara cardunculus L. BMC Plant Biology, BioMed Central, 2007, 7 (1), pp.14. 10.1186/1471-2229-7-14. hal-01738035 HAL Id: hal-01738035 https://hal.archives-ouvertes.fr/hal-01738035 Submitted on 20 Mar 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Distributed under a Creative Commons Attribution| 4.0 International License BMC Plant Biology BioMed Central Research article Open Access Isolation and functional characterization of a cDNA coding a hydroxycinnamoyltransferase involved in phenylpropanoid biosynthesis in Cynara cardunculus
    [Show full text]
  • Wine-Making with Protection of Must Against Oxidation in a Warm, Semi-Arid Terroir O
    Wine-making with Protection of Must against Oxidation in a Warm, Semi-arid Terroir o. Corona Dipartimento di Ingegneria e Tecnologie Agro-Forestali, Universita degli Studi di Palermo, 90128 Palermo, Italy Submitted for publication: November 2009 Accepted for publication: March 201 0 Key words: Enzymatic oxidation, protection against oxidation To protect varietal aromas from oxidation before alcoholic fermentation, two grape must samples were prepared from white grapes potentially low in copper, pre-cooled and supplemented with ascorbic acid and solid CO (trial 2 ) B )' AC02 or S02 (trial S02 The wines prepared from musts protected from oxidation had aroma descriptors that included "passion fruit" and "grapefruit skin". The lower concentrations offtavanols in the AC02 trial demonstrated that the use of solid CO2 as an oxidation preventative instead of S02 reduced the extraction of these polyphenols from the grape solids. The higher concentration of hydroxycinnamoyl tartaric acids of the wine from the AC02 trial with respect to BS02 was ascribed to the lower grape polyphenoloxidase activity induced by the lower oxygen level AC02 B " in the trial, or to the combination of caftaric acid quinone with the S02 in S02 Although the grapes were very ripe (alcohol in wines ~ 14.5% vol), the wines made with musts prepared by the two techniques were characterised by aroma descriptors like "passion fruit" and "grapefruit skin", and these aromas were not detected in the wines prepared from unprotected musts. F or the production of white wine, the grapes are usually pressed Darriet el aI., 1995; Bouchilloux el ai., 1998; Tominaga el ai., after destemming and crushing, and the must that is obtained after 1998; Peyrot des Gachons el ai., 2000; Murat el ai., 2001), can settling is fermented by yeasts at a temperature that generally be oxidised, with a loss of the varietal characters of the wine.
    [Show full text]
  • 5-Caffeoylquinic Acid and Caffeic Acid Orally Administered Suppress P-Selectin Expression on Mouse Platelets ⁎ Jae B
    Available online at www.sciencedirect.com Journal of Nutritional Biochemistry 20 (2009) 800–805 5-Caffeoylquinic acid and caffeic acid orally administered suppress P-selectin expression on mouse platelets ⁎ Jae B. Park Diet, Genomics, and Immunology Laboratory, BHNRC, ARS, USDA, Beltsville, MD 20705, USA Received 15 February 2008; received in revised form 18 July 2008; accepted 25 July 2008 Abstract Caffeic acid and 5-caffeoylquinic acid are naturally occurring phenolic acid and its quinic acid ester found in plants. In this article, potential effects of 5-caffeoylquinic acid and caffeic acid on P-selectin expression were investigated due to its significant involvement in platelet activation. First, the effects of 5-caffeoylquinic acid and caffeic acid on cyclooxygenase (COX) enzymes were determined due to their profound involvement in regulating P-selectin expression on platelets. At the concentration of 0.05 μM, 5-caffeoylquinic acid and caffeic acid were both able to inhibit COX-I enzyme activity by 60% (Pb.013) and 57% (Pb.017), respectively. At the same concentration, 5-caffeoylquinic acid and caffeic acid were also able to inhibit COX-II enzyme activity by 59% (Pb.012) and 56% (Pb.015), respectively. As expected, 5-caffeoylquinic acid and caffeic acid were correspondingly able to inhibit P-selectin expression on the platelets by 33% (Pb.011) and 35% (Pb.018), at the concentration of 0.05 μM. In animal studies, 5-caffeoylquinic acid and caffeic acid orally administered to mice were detected as intact forms in the plasma. Also, P-selectin expression was respectively reduced by 21% (Pb.016) and 44% (Pb.019) in the plasma samples from mice orally administered 5-caffeoylquinic acid (400 μg per 30 g body weight) and caffeic acid (50 μg per 30 g body weight).
    [Show full text]
  • Production of Verbascoside, Isoverbascoside and Phenolic
    molecules Article Production of Verbascoside, Isoverbascoside and Phenolic Acids in Callus, Suspension, and Bioreactor Cultures of Verbena officinalis and Biological Properties of Biomass Extracts Paweł Kubica 1 , Agnieszka Szopa 1,* , Adam Kokotkiewicz 2 , Natalizia Miceli 3 , Maria Fernanda Taviano 3 , Alessandro Maugeri 3 , Santa Cirmi 3 , Alicja Synowiec 4 , Małgorzata Gniewosz 4 , Hosam O. Elansary 5,6,7 , Eman A. Mahmoud 8, Diaa O. El-Ansary 9, Omaima Nasif 10, Maria Luczkiewicz 2 and Halina Ekiert 1,* 1 Chair and Department of Pharmaceutical Botany, Faculty of Pharmacy, Jagiellonian University, Medical College, ul. Medyczna 9, 30-688 Kraków, Poland; [email protected] 2 Chair and Department of Pharmacognosy, Faculty of Pharmacy, Medical University of Gdansk, al. gen. J. Hallera 107, 80-416 Gda´nsk,Poland; [email protected] (A.K.); [email protected] (M.L.) 3 Department of Chemical, Biological, Pharmaceutical and Environmental Sciences, University of Messina, Viale Palatucci, 98168 Messina, Italy; [email protected] (N.M.); [email protected] (M.F.T.); [email protected] (A.M.); [email protected] (S.C.) 4 Department of Food Biotechnology and Microbiology, Institute of Food Sciences, Warsaw University of Life Sciences—SGGW, ul. Nowoursynowska 159c, 02-776 Warsaw, Poland; [email protected] (A.S.); [email protected] (M.G.) 5 Plant Production Department, College of Food and Agricultural Sciences, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia; [email protected] 6 Floriculture, Ornamental Horticulture,
    [Show full text]
  • Phenolic Compounds in Lycopersicon Esculentum L
    Running title: Phenolic compounds in Lycopersicon esculentum L. Characterization and quantification of phenolic compounds in four tomato (Lycopersicon esculentum L.) farmer’ varieties in Northeastern Portugal homegardens Lillian Barros1,2,a, Montserrat Dueñas2,a, José Pinela1, Ana Maria Carvalho1, Celestino Santos Buelga2,*, Isabel C.F.R. Ferreira1,* 1CIMO/Escola Superior Agrária, Instituto Politécnico de Bragança, Campus de Santa Apolónia, Apartado 1172, 5301-855 Bragança, Portugal. 2Grupo de Investigación en Polifenoles (GIP-USAL), Facultad de Farmacia, Universidad de Salamanca, Campus Miguel de Unamuno, 37007 Salamanca, Spain. * Authors to whom correspondence should be addressed (e-mail: [email protected]; telephone +34 923 294537; fax +34 923 294515; e-mail: [email protected], telephone +351273303219, fax +351273325405). A Both authors contributed equally 1 Abstract Tomato (Lycopersicon esculentum L.) is one of the most widely consumed fresh and processed vegetables in the world, and contains bioactive key components. Phenolic compounds are one of those components and, according to the present study, farmer’ varieties of tomato cultivated in homegardens from the northeastern Portuguese region are a source of phenolic compounds, mainly phenolic acid derivatives. Using HPLC-DAD-ESI/MS, it was concluded that a cis p-coumaric acid derivative was the most abundant compound in yellow (“Amarelo”) and round (“Batateiro”) tomato varieties, while 4-O-caffeolyquinic acid was the most abundant one in long (“Comprido”) and heart (“Coração”) varieties. The most abundant flavonoid was quercetin pentosylrutinoside in the four tomato varieties. Yellow tomato presented the highest levels of phenolic compounds (54.23 µg/g fw), including phenolic acids (43.30 µg/g fw) and flavonoids (10.93 µg/g fw).
    [Show full text]
  • Evaluation of Cinnamic Acid and Six Analogues Against Eggs and Larvae of ⋆ Haemonchus Contortus T
    Veterinary Parasitology 270 (2019) 25–30 Contents lists available at ScienceDirect Veterinary Parasitology journal homepage: www.elsevier.com/locate/vetpar Research paper Evaluation of cinnamic acid and six analogues against eggs and larvae of ⋆ Haemonchus contortus T Gabriela Mancilla-Montelongoa, Gloria Sarahi Castañeda-Ramírezb, ⁎ Juan Felipe de Jesús Torres-Acostab, Carlos Alfredo Sandoval-Castrob, , Rocío Borges-Argáezc a CONACYT – Facultad de Medicina Veterinaria y Zootecnia, Universidad Autónoma de Yucatán, Km 15.5 Carretera Mérida-Xmatkuil, CP 97100, Mérida, Yucatán, Mexico b Facultad de Medicina Veterinaria y Zootecnia, Universidad Autónoma de Yucatán, Km 15.5 Carretera Mérida-Xmatkuil, CP 97100, Mérida, Yucatán, Mexico c Centro de Investigación Científica de Yucatán, Calle 43 No. 130 × 32 Colonia Chuburná de Hidalgo, CP 97205, Mérida, Yucatán, Mexico ARTICLE INFO ABSTRACT Keywords: This study evaluated the in vitro anthelmintic (AH) activity of cinnamic acid and six analogues against eggs and Haemonchus contortus larvae of Haemonchus contortus. Stock solutions of each compound (trans-cinnamic acid, p-coumaric acid, caffeic Nematode acid, trans-ferulic acid, trans-sinapic acid, 3,4-dimethoxycinnamic acid, and chlorogenic acid) were prepared in Egg hatch test PBS:Tween-20 (1%) for use in the egg hatch test (EHT) and larval exsheathment inhibition test (LEIT) at different Larval exsheathment inhibition test concentrations (25–400 μg/mL). The respective effective concentration 50% (EC ) values with 95% confidence Cinnamic acid analogues 50 intervals were estimated. Mixtures made of all cinnamic acid and its analogues as well as some selected in- Chemical standards dividual compounds were also tested in the EHT. Only ferulic and chlorogenic acids showed AH activity in the EHT (EC50: 245.2 μg/mL (1.26 mM) and 520.8 μg/mL (1.47 mM), respectively) (P < 0.05).
    [Show full text]
  • Consumption of Chlorogenic Acids Through Coffee and Health Implications
    beverages Review Consumption of Chlorogenic Acids through Coffee and Health Implications Adriana Farah * and Juliana dePaula Lima Laboratório de Química e Bioatividade de Alimentos e Núcleo de Pesquisa em Café (NUPECAFÉ), Instituto de Nutrição, Universidade Federal do Rio de Janeiro, Avenida Carlos Chagas Filho, 373, CCS, Bl. J, Rio de Janeiro 21941-902, Brazil; [email protected] * Correspondence: [email protected]; Tel.: +55-21-39386449 Received: 11 December 2018; Accepted: 15 January 2019; Published: 1 February 2019 Abstract: Chlorogenic acids (CGA) are the main antioxidant compounds in the Western diet, due to their high concentrations in coffee associated with the high consumption of the beverage. Until about 10 years ago, like many other phenolic compounds, CGA were thought to be poorly absorbed in the human digestive system. Along the years, large amounts of information on the absorption and metabolism of these compounds have been unveiled, and today, it is known that, on average, about one third of the consumed CGA from coffee is absorbed in the human gastrointestinal tract, although large inter-individual variation exists. Considering results from in vitro animal and human studies, it is possible to conclude that the antioxidant and anti-inflammatory effects of coffee CGA are responsible for, at least to a certain extent, the association between coffee consumption and lower incidence of various degenerative and non-degenerative diseases, in addition to higher longevity. Keywords: chlorogenic acids; coffee beverages; consumption; health effects 1. Introduction Chlorogenic acids (CGA), esters of trans-hydroxycinnamic acids and quinic acid (Figure1), were discovered in 1837 [1]. They were first thought to be caffetannic acid [2], which was in fact a mixture of different acids.
    [Show full text]
  • Chlorogenic Acid and Its Relationship with Lignin Biosynthesis
    UNIVERSIDADE ESTADUAL DE CAMPINAS INSTITUTO DE BIOLOGIA Nathalia Volpi e Silva CHLOROGENIC ACID AND ITS RELATIONSHIP WITH LIGNIN BIOSYNTHESIS ÁCIDO CLOROGÊNICO E SUA RELAÇÃO COM A BIOSSÍNTESE DE LIGNINA CAMPINAS - SP 2019 NATHALIA VOLPI E SILVA CHLOROGENIC ACID AND ITS RELATIONSHIP WITH LIGNIN BIOSYNTHESIS ÁCIDO CLOROGÊNICO E SUA RELAÇÃO COM A BIOSSÍNTESE DE LIGNINA Thesis presented to the Institute of Biology of the University of Campinas in partial fulfillment of the requirements for the degree of Doctor in Genetic and Molecular Biology in the area of Plant Genetics and Breeding. Tese apresentada ao Instituto de Biologia da Universidade Estadual de Campinas como parte dos requisitos exigidos para obtenção do Título de Doutor em Genética e Biologia Molecular, na área de Genética Vegetal e Melhoramento. Supervisor / Orientador: Prof. Dr. Paulo Mazzafera Co-supervisor / Co-Orientador: Prof. Dr. Igor Cesarino ESTE ARQUIVO DIGITAL CORRESPONDE À VERSÃO FINAL DA TESE DEFENDIDA PELA ALUNA NATHALIA VOLPI E SILVA, ORIENTADA PELO PROF. DR. PAULO MAZZAFERA. CAMPINAS - SP 2019 Agência de fomento: FAPESP Agência de fomento: Capes N° Processo: 2014/17831-5, 2016/15834-2 N° Processo: 001 Nº processo:0 Nº processo:0 Campinas, 31de julho de 2019 EXAMINATION COMMITTEE Banca examinadora Dr. Paulo Mazzafera (Supervisor/Orientador) Dr. Paula Macêdo Nobile Dra. Sara Adrian Lopez de Andrade Dr. Douglas Silva Domingues Dr. Michael dos Santos Brito Os membros da Comissão Examinadora acima assinaram a Ata de Defesa, que se encontra no processo de vida acadêmica do aluno. ACKNOWLEDGMENT I would like to thank the São Paulo Research Foundation (Fundação de Amparo à Pesquisa do Estado de São Paulo) Grant (Processo) nº 2014/17831-5, FAPESP and n° 2016/15834-2, FAPESP for the grant/fellowship and all financial support to develop this thesis.
    [Show full text]
  • Production of Native Plants for Seed, Biomass, and Natural Products A
    Production of native plants for seed, biomass, and natural products A Dissertation SUBMITTED TO THE FACULTY OF UNIVERSITY OF MINNESOTA BY Katrina Franziska Freund Saxhaug IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY Craig C. Sheaffer, advisor March 2020 © Katrina Franziska Freund Saxhaug 2019 Acknowledgements The research presented in this document would not have been possible without the love and support of countless mentors, colleague, friends and family. Foremost, I am forever grateful to my advisor, Dr. Craig Sheaffer, whose direction, support, understanding, and unending generosity made it possible for me to complete my doctorate. I am also eternally thankful for my unofficial co-advisor, Dr. Adrian Hegeman, for his kindness, intellectual brilliance, and support throughout my degree program. I am also incredibly grateful to Dr. Susan Galatowitsch and Dr. Clay Carter for their guidance, wisdom, and constructive and insightful commentaries. Though not on my committee, Dr. Jacob Jungers was incredibly generous with his time, advice, and support in all aspects of this research. While a doctoral student, I was supported by grants from the Minnesota Department of Agriculture through the AGRI Crop Research Grant Program and the Specialty Crop Block Grant Program. Additional support came through the Minnesota Institute for Sustainable Agriculture gift fund, graciously provided by Leanna Forcier. Further support was provided by the University of Minnesota, including the Hueg-Harrison Graduate Fellowship, the Mark and Jean Schroepfer Fellowship, the Nancy Jo Ehlke Fellowship, and Annie’s Sustainable Agriculture Scholarship. The Sustainable Cropping Systems Lab, under the direction of Dr Craig Sheaffer, and the Plant Metabolomics Lab, under the direction of Dr.
    [Show full text]
  • AOAC SMPR® 2017.015 Standard Method Performance Requirements
    AOAC SMPR® 2017.015 Raw materials.—Fresh, dried, or cut plant material. Recovery.—The fraction or percentage of spiked analyte that is recovered when the test sample is analyzed using the entire method. Standard Method Performance Requirements Repeatability.—Variation arising when all efforts are made (SMPRs®) for Determination of Phenolic Compounds in Dietary Supplements and Dietary Ingredients to keep conditions constant by using the same instrument and Containing Echinacea operator and repeating during a short time period. Expressed as the repeatability standard deviation (SDr); or % repeatability relative standard deviation (%RSD ). Intended Use: Quality Assurance and Compliance to r Reproducibility.—The standard deviation or relative standard Current Good Manufacturing Practices (CGMPs) deviation calculated from among-laboratory data. Expressed as 1 Purpose the reproducibility standard deviation (SDR); or % reproducibility AOAC SMPRs describe the minimum recommended relative standard deviation (%RSDR). performance characteristics to be used during the evaluation of a 5 Method Performance Requirements method. The evaluation may be an on-site verification, a single- laboratory validation, or a multi-site collaborative study. SMPRs See Tables 4 and 5. are written and adopted by AOAC stakeholder panels composed of representatives from industry, regulatory organizations, contract 6 System Suitability Tests and/or Analytical Quality Control laboratories, test kit manufacturers, and academic institutions. Suitable methods will include blank check samples, and check AOAC SMPRs are used by AOAC expert review panels in their standards at the lowest point and midrange point of the analytical evaluation of validation study data for method being considered for Performance Tested MethodsSM or AOAC Official Methods of range. A control sample must be included.
    [Show full text]
  • Lamiaceae) from the Monti Sibillini National Park: a Potential Source of Bioactive Compounds
    Journal of Intercultural Ethnopharmacology www.jicep.com Original Research DOI: 10.5455/jice.20170327073801 Reassessment of the polar fraction of Stachys alopecuros (L.) Benth. subsp. divulsa (Ten.) Grande (Lamiaceae) from the Monti Sibillini National Park: A potential source of bioactive compounds Alessandro Venditti1, Claudio Frezza2, Lorenzo M. Lorenzetti1, Filippo Maggi3, Mauro Serafini2, Armandodoriano Bianco1 1Department of ABSTRACT Chemistry, Sapienza Background: The phytochemical analysis of Stachys alopecuros subsp. divulsa, an endemic Italian species, has University of Rome, been recently reported and has showed the presence of 8-O-acetylharpagide (2), harpagide (3), allobetonicoside (4), Rome, Italy, 2Department of Environmental Biology, and 4′-O-galactopyranosyl-teuhircoside (5). In this paper, an in deep study of its glycosidic fraction with the aim to Sapienza University widen the knowledge on its secondary metabolites content is reported. Materials and Methods: Chromatographic of Rome, Rome, Italy, techniques were used for the isolation of constituents while spectroscopic and spectrometric techniques were 3School of Pharmacy, applied for the structures elucidation. Results: Besides the known constituents, all of them reconfirmed, Università di Camerino, ajugoside (1), reptoside (6) and 6-O-acetyl-ajugol (7) were also identified among the iridoids while the phenolic Camerino, Italy components resulted to be chlorogenic acid (8), β-arbutin (9), verbascoside (10), and stachysoside A (11), instead. Conclusion: The iridoid pattern of S. alopecuros subsp. divulsa has been expanded with the identification of not Address for correspondence: Alessandro Venditti, previously reported compounds as well as for the phenolic fraction. Except for the reconfirmed verbascoside (10), Dipartimento di Chimica, the other phenolic compounds were recognized for the first time in the studied species.
    [Show full text]
  • Phenolic Compounds Profile and Antioxidant Capacity of Pitahaya
    foods Article Phenolic Compounds Profile and Antioxidant Capacity of Pitahaya Fruit Peel from Two Red-Skinned Species (Hylocereus polyrhizus and Hylocereus undatus) Wanpei Tang 1,†, Wu Li 1,† , Yuzhe Yang 2, Xue Lin 1,* , Lu Wang 1, Congfa Li 1 and Ruili Yang 2,* 1 Key Laboratory of Food Nutrition and Functional Food of Hainan Province, College of Food Science and Engineering, Hainan University, Haikou 570228, China; [email protected] (W.T.); [email protected] (W.L.); [email protected] (L.W.); [email protected] (C.L.) 2 College of Food Science, South China Agricultural University, Guangzhou 510642, China; [email protected] * Correspondence: [email protected] (X.L.); [email protected] (R.Y.); Tel.: +86-898-6619-8861 (X.L.); +86-20-8528-3448 (R.Y.) † These authors contributed equally to this article. Abstract: Pitahaya peel is a good source of bioactive polyphenols. However, the bound phenolics and their antioxidant activity remain unclear. The bound phenolics of pitahaya peel from two red-skinned species with red pulp (RP) and white pulp (WP) were released with different methods (acid, base, and composite enzymes hydrolysis). The results revealed that base hydrolysis was the most efficient method for releasing the bound phenolics from RP (11.6 mg GAE/g DW) and WP (10.5 mg GAE/g DW), which was 13.04-fold and 8.18-fold for RP and 75.07-fold and 10.94-fold for WP compared with acid hydrolysis and enzymatic hydrolysis, respectively. A total of 37 phenolic compounds were identified by UPLC-TOF/MS with most chlorogenic acid, caffeic acid, ferulic acid and p-coumaric Citation: Tang, W.; Li, W.; Yang, Y.; Lin, X.; Wang, L.; Li, C.; Yang, R.
    [Show full text]