DOCSLIB.ORG

In Partial Fulfillment

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
In Partial Fulfillment PHYTOCHB}ÍTCAL I}WBSTIG¡,TION OF TRITICALE EJìGOT by RICHATD PETER I4OSZYNSIfl 0ctober 1971 A Thesis Presented to Lhe Faeulty of Graduate Studies UniversitY of ì'fanitoba In Partial Fulfillment of the Requi-rernents for the Degree llaster of Science in Pharmacy ACKNOI\ILEDGEMENTS The author wishes No express his sincere appreciaLion Lo the follovrings Dr. R.C.S" Audette for his supervisionu encouragement, and patience during the course of this sludy; Dr' J' Templeton for his friendly assistanceo his colleagues in the Faculty of Pharmacy at the University of }fanitoba for many useful discussions; trliss Rosella Enns for Ìrer technieal assisLance; and }fr" A1 Arnott of Darlingford, .Ìdanitoba for the supply of Triticale ergot (Rosner cultivar) ' The author also gratefull)'aelnnowledges the receipt of the CanadÍan Foundatíon for the Advaneement of Pharmacy Graduate Students Fellor^¡ship (ffZO)u Nhe fi,naneial assistance provicled by Dr' R"C" l4cÏnnis and the DeparLnent of Plant Science at the university of Ì'lanitobau and the teaching assistantship provided by the Faculty of Pharrnacy at the University of I'fa'nitoba" ABSTRACT PIITTOCHE}{ICAL INVESTIGATION OF TRITICAIÐ ERGOT by RICHARD PETER MOSZYNShT Ergot g,)i.o'rit1 on lritieale grain (Rosner eultivar) v¡as ín¡,'estiga+.ed w.íLh regard to morphologieal characterisLícsu fat eonLent and alk"aloj-d eonterrt (quan'bitative a.nd o,uatitative)" Soxhlet extraction of the porvdered. ergot sample using petroleum ether yiel-ded 16,74% v/w of ergot oil" The total alkaloid content of the sampl€ tfås detennined by a colorimetric assay procedure to be 0'181%' The rrrater-soluble and rqater-insoluble alkaloids constituLed 2A/" and 8Aà of total alkaloids respectively. The ergot alkaloids extraebed from the sample Ïrere separa.ted on a tartaric acid Ímpregnated cellulose column into the peptide alka.loid fractionu the clavine alkaloid fraetÍon and ergometrine" Subsequent thin-la},er chromatography and paper chrornatography of these fraetions identified. ergotamine, the ergotoxine groupe ergometrine, a trace of ergometrinine, penniclavine, setoclaviue, elymoclavine, agroclavine and possibly isopennielavine" The alkaloi-ds from tr,¡o of the cellulose column fractions trere purified and characterized. The melting points, Í:nfra'red, nuclear magnetic resonanceu and nass spectra of the isolated alkaloicis v¡ere recorded" The all<aloid.s lt'ere id-enlified as ergotanine and ergometrirren TABLE OF CONTENT r_l-r Page TNTRODUCTIO[] Claviceps Purpurea I Alkaloids of qlavlqS:ge PuIPure+ I Peptide Alkaloids 3 Clavine A1kaloids I Tbiticale I3 Triticale Ergot L6 ffiPERT}MNTAL 18 T. I'ÍATEMALS Solvents 18 Chemicals 18 Adsorbents I9 fnstruments 19 EquiPment 20 II. I{ORPHOT¡GICAI ÐIA],rINATION 2L 23 III. FAT ASSAY Results and Discussion 23 28 IV" AI,KALOTDAI, ASSAY Results and Discussion 3L VU COITÌ'ÍN CHROI,IATOGRAPTIY 3l+ Results and Discussion )o VI. ÎHIN_LÂITR CHROJ{ATOGRAPIIY 40 FreParation of Adsorbents 40 Preparation of van Urk Spray Reagent l+I 1V Pn oø Basic TLC of Colu¡rn FractÍons 41 TLC of Fraction B U+ l+7 TLC of Fraction C GLC of Fraction C 5L TLC of Fraction E 48 fLC of Fraction I 5L WT. PAPER CHRO]"IATOGRA?HY 53 For"namid.e /øenzene fPetroleum Ether System 53 Fonnamide /nenzene fPyridine Systern 5l+ i[IT.PURIFICATIONOFTSOL¡.TEDERGOTAJ,I{ALOIDS 56 Fraction B (Ergota¡'rine) 56 Fraetion I (Ergornetrine) 56 IX'CHARAOTERIZATIONOFISOLATBDBRGOTALK¿IOIDS 58 Melting Point Determination 58 J¡frared Spectra 59 Nuclear l''lagnetic Resonance Spectra 62 l{ass Spectra 67 v IIST OF TABLES PAGE Iu Tþes of Peptide Alkaloids b 2, Chemical and Physical Characteristics of Peptide Alkaloids , 6 3, Solubilities and l'[elting Points of Peptide Alkaloids 7 l+, Chemical and Fhysical Characteristics of Clavine Alkaloids L0 5" Solubilities and I'felting Points of Clavine Alkaloids 11 6. Results of Fat AssaYs 2l+ Fat Content of Ergot Samples 7 " Comparison of from Various Hosts and Locations 25 8" Characteristics of Ergot Oil 26 g" ComparÍson of Ergot, Oil Fatty Acid Compositd-on 27 10" Cornparíson of Alkaloid Content of Ergot on Different Hosts and fron Different Locaùions 32 11, Fractions Collected from Cellulose Colwm 38 L2, Fraetions conbined from lartaric Acid Impregnated Cellulose Column 4Z L3, R, x 1OO Values of Ergot Alkaloids in t'tethanol/Chloroforn on Silica GeI GF h5 Il+" TLC Results of Fraci;ion B Obtained from Cellul-ose Cotumn b6 v] PAGE L5, TLC Results of Fraction C Obtained from Cellulose Column l+7 16" fLC Results of Fraction E Obtained fron Ce]-lulose Column l+9 ].7, TLC Results of Fraction I Obtained from Cellulose Co1umn 52 18, Meltj¡e Points of Isolated lllkaloids 58 val LTST OF FTGURES PAGB 1, Structure of Ergoli¡e 3 2n Stmcture of d-Lysergic Acid ) 3" Structure of d-Isolysergic Acid 3 4. General Structure of Peptide A1kaloids 5 5. Structure of Ergotmerine I 6" General Stmcture of Clavine Alkaloids I 7" UuV" Spectrum of Ergot Alkaloids 1t 8" Procedure for AJ-kal-oid Assay 3O 9u Development of Column 35 10, Elution of Alkaloids from Cellulose Column 37 11, Basic TLC of Column Fractions l+3 1*2. Paper Chron:atography of Clarrine Alkaloids 55 Lj" IR Spectrum of Ergotan,ine 6o 14" IR Spectrum of Fraction B 6o l-5" IR Spectrum of Ergometrine l'hleate 61 16" IR Spectrum of Fraction I 6L L7 " NÌ4R Spectrum of Fraction I 63 18" Nì4R Spectrum of Ergonetrine þfaleate 6l+ 19, Nl'fiì Spectrum of Fraetion B 65 20, Nl'fR Spectrum of Ergotarnine 66 2L" lrtass Spectrrrm of Ergometrine l4aleate 69 22" }4ass Spectnrm of Fraction I 7O 23" lt{ass Spectrun of Ergotamine 7I 2k, ltfass Spectrum of Fraction B 72 25, Decomposition Sequence of llrgornet,rine ?3 INTRODUCTIOÀT -1- ClavicepsJurpurea Claviceps purpu{ea (Fries) Ti:lasne (famS-fy H¡rpocreaceae, Class Asconycetes) is a parasitic fungus eommonly occurrlng on grasses and cr-rlti: vaLecl eerealsn Ergot of commerce is defined as the drled sclerotiumt or resting stage of Clavieeps Þl¡Ipurea - a hard, purplish, somewhat curved bodyu the size of which is usually cleternined by the size of the grain it parasitizes (1). The generie name Claviceps refers to the club-like charaet,er of the sclerot,iun, purpJ¡.rqa to its purple color (2)" orÍginalIy, the main sources of supply for ergot were spainu Russia and the Bal-kan countries; horrever, Russia and the Balkans export very litt]e ergot today, Currentlyu eonsiderable ergot is being cultivated in Czechoslovakia, Germany, Hungary and Switzertand (2)' other species of clavicqpg are eapable of producing ergots in the ovaries of many other members of the Granrineae fanily sueh as Triticumu Avena, Festuea, Lolium, l'Íolinia ancl Nardus (3 ), A1ka1o1 since galenical preparations of the crude drug are seldont employed in pharmacy in this countr¡r, ergot has been omitted from the offfcial compendia" Neverthelessu the ergot alkaloÍds conLinue to enJoy r,ridespread use as extremely important medieinal agents (2). t"lore than a score of alkaloids have been isolated from the fungUs , -2- Clavicep_s pul-pul:eae growing as a parasiLe on various members of the G::amineae (grasses) family, the nost important of r','ìrich are ergometri-ne, ergotarnine, an¿ a mixLure of ergocornine, ergocri-stine, and ergocryptine (6)" The average content of total alkaloids in the sclero{,ia vari-es between O.OZ5 and. O"t+% but the all<aloid content of individual sclerotia ís also variable; some sclerotia containj-ng very little all<aloidu whÍIe others may contain as much as y/, ß)" The qualitative and quantitative composition of the alkaloids obtained fi'om different hosb plants or grown in saprophytic culture is influenced by a nu¡nber of factors but especially by the iclentíty of the strain of the organism involved (2)" Both peptide alkaloids and nonpeptide (r^,ater-soluble) al-kal-oids were obtained. from parasitically developed ergot selerotia, l,''irile only the r¿ater-solubre tlpe was produced commereiall¡' in saprophytic culture" In 1969u however, l¡rici e! gI, (å.) succeedecl in isola.ting three sLrains of Clavicepq_ pqqruleQ. from selerotia groi,¡fi on rye r'ùich produced, under" subrnerged saprophyt,ic conditionsu ergocr¡ptíne and ergotamine, ergocornine and ergosineu and ergoeristine, respeetively' Large seale production of lysergic aeicì derivatives in submerged culture was achieved in 1960 by Tonolo, Chain and co*i,¡orkers in Italy (Z)" These inves'bigators ul,ilizecl a st,rain of. kl¡æÈg._p*È*slgÀ! i+ìrich procìuced severa.l simple lysergie acid derivatives (2). The ergot alkaloids belong 1,o 'r,he large" significant class of the indole all<aloids and posses$ a teLracycl-ic ring sysLen named ergoline (pígure t) " AIl of the ergot alkal-oids possess this chai"acierisLic base s|ructure (5), -3- 7 D óñ r0 H 5 H HN I Figqle]. Ergoline The natural ergot alkaloids ean be classified into trqc main groups according to their basic chenrical structure; the peptide alkaloidsu and the clavine alkaloids (5)" Tre peptíde or v,ater-insoluble aIl<aloidse are derivatives of d-lysergic acid (figure Z)" Since this compound j.s readily converted to its isomer, d-isolysergic acid (¡'igure 3), corresponding isol¡'sergic N-CH3 d:IqoLys-ergiq.rLc-id Ei gug!" d-LyserBi" Auiu Eieufg 3. -l+ - acid derivatives often acconpany the d-lysergic acid alkaloids in the natural material or are produced during the course of extraction" These peptide alkaloids are aeid amide derivatives of the basic d-lysergic or d-isolysergie structure and consequently yieId, on alkaline hydrolysis, d-lysergic or d-isolysergic acid, The individual alkaloids in this group differ only in the
Load more

Recommended publications
  • Nematotoxicity of Neotyphodium Infected Tall Fescue Alkaloids and Other Secondary Metabolites on Pratylenchus Scribneri
    NEMATOTOXICITY OF NEOTYPHODIUM-INFECTED TALL FESCUE ALKALOIDS AND OTHER SECONDARY METABOLITES ON THE PLANT- PARASITIC NEMATODE PRATYLENCHUS SCRIBNERI by ADA ANTONIA BACETTY (Under the direction of Charles W. Bacon) ABSTRACT Tall fescue (Festuca arundinacea) is a perennial, cool-season turf and forage grass species in the United States that covers over 20 million hectares of pastureland. Neotyphodium coenophialum, an endophytic fungus associated with cool-season grasses, enhances host fitness and imparts pest resistance to the grass. Biologically active alkaloids and other secondary metabolites are produced in this association that not only cause adverse effects on livestock, fescue toxicosis, but may also play a role in the reduction of plant-parasitic nematode populations. Currently there is little information available on the effects of these biologically active compounds on nematodes associated with tall fescue. Therefore, this research examines the interaction of ergot and loline alkaloids, as well as polyphenolic compounds, from endophyte-infected tall fescue on toxicity to the lesion nematode, Pratylenchus scribneri. In vitro bioassays were performed to assess the effects of specifically identified compounds on P. scribneri motility, mortality, and chemoreception. While separate greenhouse studies evaluated the effects of endophyte- infected tall fescue on P. scribneri viability. Root extracts served as nematistatic agents to the nematodes in the chemical submersion assays and affected nematode behavior by acting as repellents in chemoreception studies. During individual tests, ergovaline and α-ergocryptine were nematicidal at 5µg/ml and 50µg/ml respectively. However, chemotaxis studies revealed α-ergocryptine as an attractant (1-20µg/ml) and repellent (50-200µg/ml). Ergovaline was an effective repellent (1-5µg/ml) and a nematicidal (10-200µg/ml).
    [Show full text]
  • Ergot Alkaloid Biosynthesis in Aspergillus Fumigatus : Association with Sporulation and Clustered Genes Common Among Ergot Fungi
    Graduate Theses, Dissertations, and Problem Reports 2009 Ergot alkaloid biosynthesis in Aspergillus fumigatus : Association with sporulation and clustered genes common among ergot fungi Christine M. Coyle West Virginia University Follow this and additional works at: https://researchrepository.wvu.edu/etd Recommended Citation Coyle, Christine M., "Ergot alkaloid biosynthesis in Aspergillus fumigatus : Association with sporulation and clustered genes common among ergot fungi" (2009). Graduate Theses, Dissertations, and Problem Reports. 4453. https://researchrepository.wvu.edu/etd/4453 This Dissertation is protected by copyright and/or related rights. It has been brought to you by the The Research Repository @ WVU with permission from the rights-holder(s). You are free to use this Dissertation in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you must obtain permission from the rights-holder(s) directly, unless additional rights are indicated by a Creative Commons license in the record and/ or on the work itself. This Dissertation has been accepted for inclusion in WVU Graduate Theses, Dissertations, and Problem Reports collection by an authorized administrator of The Research Repository @ WVU. For more information, please contact [email protected]. Ergot alkaloid biosynthesis in Aspergillus fumigatus: Association with sporulation and clustered genes common among ergot fungi Christine M. Coyle Dissertation submitted to the Davis College of Agriculture, Forestry, and Consumer Sciences at West Virginia University in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Genetics and Developmental Biology Daniel G. Panaccione, Ph.D., Chair Kenneth P. Blemings, Ph.D. Joseph B.
    [Show full text]
  • Occurrence and Significance of Mycotoxins in Forage Crops And
    J Sci Food Agric 1998, 77,1È17 Occurrence and Signiücance of Mycotoxins in Forage Crops and Silage: a Review Keith A Scudamore1* and Christopher T Livesey2 1 Central Science Laboratory, London Road, Slough, Berks, SL3 7HJ, UK 2 Veterinary Laboratories Agency, New Haw, Woodham Lane, Addlestone, Surrey, KT15 3NB, UK (Received 5 December 1996; revised version received 29 May 1997; accepted 4 September 1997) Abstract: Study of mycotoxins in animal feeding stu†s has concentrated on the occurrence of aÑatoxins and, to a lesser extent, other mycotoxins in cereals, raw materials and concentrate feeds. However, ruminant diets contain a high propor- tion of forage crops such as grass or maize silage, hay and straw. Under adverse growing, production or storage conditions, fungal spoilage is likely to occur with some degree of mycotoxin contamination. The mould Ñora of forage crops is likely to di†er signiÐcantly from that of cereals and mycotoxin contamination, should it occur, could di†er qualitatively and quantitatively. Information relating to forage crops as a potential source of mycotoxins is reviewed. Some Ðeld inci- dents and animal disease which may be mycotoxin related are discussed and analytical methods are reviewed. Information on dose and e†ect of candidate mycotoxins is given where available. The review suggests areas which the authors consider merit further study. Crown Copyright 1998. J Sci Food Agric 77,1È17 (1998) Key words: mycotoxins; fungi; moulds; silage; forage crops; hay; straw; occurrence; analysis; risk assessment; animal disease INTRODUCTION access, silage will be at risk from storage moulds such as Penicillium and Aspergillus. However, moulds may be During growth, forage crops are at risk in the Ðeld from aerobic or anaerobic and this means that, even if infection by a number of di†erent fungi, some of which oxygen is excluded, some moulds may be able to may produce mycotoxins.
    [Show full text]
  • Risk Assessment of Argyreia Nervosa
    Risk assessment of Argyreia nervosa RIVM letter report 2019-0210 W. Chen | L. de Wit-Bos Risk assessment of Argyreia nervosa RIVM letter report 2019-0210 W. Chen | L. de Wit-Bos RIVM letter report 2019-0210 Colophon © RIVM 2020 Parts of this publication may be reproduced, provided acknowledgement is given to the: National Institute for Public Health and the Environment, and the title and year of publication are cited. DOI 10.21945/RIVM-2019-0210 W. Chen (author), RIVM L. de Wit-Bos (author), RIVM Contact: Lianne de Wit Department of Food Safety (VVH) [email protected] This investigation was performed by order of NVWA, within the framework of 9.4.46 Published by: National Institute for Public Health and the Environment, RIVM P.O. Box1 | 3720 BA Bilthoven The Netherlands www.rivm.nl/en Page 2 of 42 RIVM letter report 2019-0210 Synopsis Risk assessment of Argyreia nervosa In the Netherlands, seeds from the plant Hawaiian Baby Woodrose (Argyreia nervosa) are being sold as a so-called ‘legal high’ in smart shops and by internet retailers. The use of these seeds is unsafe. They can cause hallucinogenic effects, nausea, vomiting, elevated heart rate, elevated blood pressure, (severe) fatigue and lethargy. These health effects can occur even when the seeds are consumed at the recommended dose. This is the conclusion of a risk assessment performed by RIVM. Hawaiian Baby Woodrose seeds are sold as raw seeds or in capsules. The raw seeds can be eaten as such, or after being crushed and dissolved in liquid (generally hot water).
    [Show full text]
  • Regulation of Alkaloid Biosynthesis in Plants
    CONTRIBUTORS Numbers in parentheses indicate the pages on which the authors’ contributions begin. JAUME BASTIDA (87), Departament de Productes Naturals, Facultat de Farma` cia, Universitat de Barcelona, 08028 Barcelona, Spain YEUN-MUN CHOO (181), Department of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia PETER J. FACCHINI (1), Department of Biological Sciences, University of Calgary, Calgary, AB, Canada TOH-SEOK KAM (181), Department of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia RODOLFO LAVILLA (87), Parc Cientı´fic de Barcelona, Universitat de Barcelona, 08028 Barcelona, Spain DANIEL G. PANACCIONE (45), Division of Plant and Soil Sciences, West Virginia University, Morgantown, WV 26506-6108, USA CHRISTOPHER L. SCHARDL (45), Department of Plant Pathology, University of Kentucky, Lexington, KY 40546-0312, USA PAUL TUDZYNSKI (45), Institut fu¨r Botanik, Westfa¨lische Wilhelms Universita¨tMu¨nster, Mu¨nster D-48149, Germany FRANCESC VILADOMAT (87), Departament de Productes Naturals, Facultat de Farma` cia, Universitat de Barcelona, 08028 Barcelona, Spain vii PREFACE This volume of The Alkaloids: Chemistry and Biology is comprised of four very different chapters; a reflection of the diverse facets that comprise the study of alkaloids today. As awareness of the global need for natural products which can be made available as drugs on a sustainable basis increases, so it has become increas- ingly important that there is a full understanding of how key metabolic pathways can be optimized. At the same time, it remains important to find new biologically active alkaloids and to elucidate the mechanisms of action of those that do show potentially useful or novel biological effects. Facchini, in Chapter 1, reviews the significant studies that have been conducted with respect to how the formation of alkaloids in their various diverse sources are regulated at the molecular level.
    [Show full text]
  • Phoretic Analysis of Ergot Alkaloids. Relations Mobility in the Cle Vine
    Acta Pharm, Suecica 2, 357 (1965) Thin-layer chromatographic and thin-layer electro- phoretic analysis of ergot alkaloids.Relations between structure, RM value and electrophoretic mobility in the cle vine series STIG AGUREll DepartMent of PharmacOgnosy, Kunql, Farmaceuliska Insiitutei, StockhOLM, Sweden SUMMARY A thin-layer chromatographic and electrophoretic study of the ergot alkaloids has been made, to find rapid methods for the separation and identification of the known ergot alkaloids. The mobilities of ergot alkaloids in several useful chromatographic and electrophore- tic systems are recorded. Relations have been observed between structure and R" value in methanol-chloroform on Silica Gel G. A simple, rapid thin-layer electrophoretic technique has been de- vised for separation of ergot alkaloids, and a relation between structure and electrophoretic mobility is evident. Two-dimensional combinations of thin-layer chromatography and thin-layer electro- phoresis and chromatography are described. Numerous paper chromatographic procedures have been published for separation of the ergot alkaloids and their derivatives. Hofmann (1) and Genest & Farmilio (2) have recently listed these systems. The general advantages of thin-layer chromatography (TLC) over paper partition chromatography are well known: shorter time of equilibration and devel- opment, generally better resolution, smaller amounts of substance rc- quired, and wider choice of reagents. Several reports of TLC of ergot alkaloids have been published. In gene- ral, these investigations (2-6 and others) have dealt 'with limited groups of alkaloids, or with a specific problem involving at most a dozen of the 40 now known naturally occurring ergot alkaloids. Some paper chromate- .357 graphic systems using Iorrnamide-treated papers have also been adopted for thin-layer chromatographic use (7, 8).
    [Show full text]
  • Electronic Supplementary Material (ESI) for RSC Advances. This Journal Is © the Royal Society of Chemistry 2017
    Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2017 The physicochemical properties and NMR spectra of some ergot alkaloids are summarized as following. Especially, under the influence of acids, alkaloids or light, the carbo at the position 8 of D-lysergic acid derivatives can occur isomerization which 8R is changed into 8S to form the responding isomers, lead to the formation of α-ergotaminine, ergocryptinine, ergocorninine and ergocristinine which the NMR data are shown in Table S1, S2 and S3. Clavine Agroclavine: crystal (acetone), mp 198~203℃, soluble in benzene, ethanol, slightly soluble 1 in water. Molecular formula: C16H18N2, MW m/z: 238. The data of H-NMR (Pyridine-d5，220 13 MHz) and C-NMR (Pyridine-d5，15.08 MHz) {Bach, 1974 #48}are shown in Table S1 and S2. Elymoclavine: mp 250~252℃, Molecular formula: C16H18N2O, MW m/z: 254. The data of 1 13 H-NMR (CDCl3, 220 MHz) and C-NMR (CDCl3, 15.08 MHz){Bach, 1974 #48} of its acetate derivatives are shown in Table S1 and S2. 1 Festuclavine: mp 241℃, Molecular formula: C16H18N2, MW m/z: 238. The data of H-NMR 13 (CDCl3, 220 MHz) and C-NMR (CDCl3, 15.08 MHz) {Bach, 1974 #48}are shown in Table S1 and S2. Fumigaclavine B: mp 265~267℃, Molecular formula: C16H20N2O, MW m/z: 256. The data of 1 13 H-NMR (pyridine-d5，220 MHz) and C-NMR (pyridine-d5，15.08 MHz) {Bach, 1974 #48}are shown in Table S1 and S2. Ergoamides Ergometrine: white crystal (acetone), mp 162℃.
    [Show full text]
  • Diversification of Ergot Alkaloids in Natural and Modified Fungi
    Toxins 2015, 7, 201-218; doi:10.3390/toxins7010201 OPEN ACCESS toxins ISSN 2072-6651 www.mdpi.com/journal/toxins Review Diversification of Ergot Alkaloids in Natural and Modified Fungi Sarah L. Robinson and Daniel G. Panaccione * Division of Plant and Soil Sciences, West Virginia University, Morgantown, WV 26506, USA; E-Mail: [email protected] * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +1-304-293-8819; Fax: +1-304-293-2960. Academic Editor: Christopher L. Schardl Received: 21 November 2014 / Accepted: 14 January 2015 / Published: 20 January 2015 Abstract: Several fungi in two different families––the Clavicipitaceae and the Trichocomaceae––produce different profiles of ergot alkaloids, many of which are important in agriculture and medicine. All ergot alkaloid producers share early steps before their pathways diverge to produce different end products. EasA, an oxidoreductase of the old yellow enzyme class, has alternate activities in different fungi resulting in branching of the pathway. Enzymes beyond the branch point differ among lineages. In the Clavicipitaceae, diversity is generated by the presence or absence and activities of lysergyl peptide synthetases, which interact to make lysergic acid amides and ergopeptines. The range of ergopeptines in a fungus may be controlled by the presence of multiple peptide synthetases as well as by the specificity of individual peptide synthetase domains. In the Trichocomaceae, diversity is generated by the presence or absence of the prenyl transferase encoded by easL (also called fgaPT1). Moreover, relaxed specificity of EasL appears to contribute to ergot alkaloid diversification. The profile of ergot alkaloids observed within a fungus also is affected by a delayed flux of intermediates through the pathway, which results in an accumulation of intermediates or early pathway byproducts to concentrations comparable to that of the pathway end product.
    [Show full text]
  • Impact of Ergot Alkaloid and Estradiol 17B on Whole-Body Protein Turnover and Expression of Mtor Pathway Proteins in Muscle of Cattle
    University of Kentucky UKnowledge Theses and Dissertations--Animal and Food Sciences Animal and Food Sciences 2020 Impact of Ergot Alkaloid and Estradiol 17B on Whole-Body Protein Turnover and Expression of mTOR Pathway Proteins in Muscle of Cattle Taylor Dawn Ferguson University of Kentucky, [email protected] Author ORCID Identifier: https://orcid.org/0000-0001-6598-4133 Digital Object Identifier: https://doi.org/10.13023/etd.2020.459 Right click to open a feedback form in a new tab to let us know how this document benefits ou.y Recommended Citation Ferguson, Taylor Dawn, "Impact of Ergot Alkaloid and Estradiol 17B on Whole-Body Protein Turnover and Expression of mTOR Pathway Proteins in Muscle of Cattle" (2020). Theses and Dissertations--Animal and Food Sciences. 122. https://uknowledge.uky.edu/animalsci_etds/122 This Master's Thesis is brought to you for free and open access by the Animal and Food Sciences at UKnowledge. It has been accepted for inclusion in Theses and Dissertations--Animal and Food Sciences by an authorized administrator of UKnowledge. For more information, please contact [email protected]. STUDENT AGREEMENT: I represent that my thesis or dissertation and abstract are my original work. Proper attribution has been given to all outside sources. I understand that I am solely responsible for obtaining any needed copyright permissions. I have obtained needed written permission statement(s) from the owner(s) of each third-party copyrighted matter to be included in my work, allowing electronic distribution (if such use is not permitted by the fair use doctrine) which will be submitted to UKnowledge as Additional File.
    [Show full text]
  • 3.3.11 Synthesis of Lysergic Acid Diethylamide by Vollhardt...67
    Copyright by Jason Anthony Deck 2007 The Dissertation Committee for Jason Anthony Deck certifies that this is the approved version of the following dissertation: Studies Towards the Total Synthesis of Condylocarpine and Studies Towards the Enantioselective Synthesis of (+)-Methyl Lysergate Committee: Stephen F. Martin, Supervisor Philip D. Magnus Michael J. Krische Richard A. Jones Sean M. Kerwin Studies Towards the Total Synthesis of Condylocarpine and Studies Towards the Enantioselective Synthesis of (+)-Methyl Lysergate by Jason Anthony Deck, B.S.; M.S. Dissertation Presented to the Faculty of the Graduate School of The University of Texas at Austin in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy The University of Texas at Austin May 2007 Studies Towards the Total Synthesis of Condylocarpine and Studies Towards the Enantioselective Synthesis of (+)-Methyl Lysergate Publication No. _______ Jason Anthony Deck, PhD The University of Texas at Austin, 2007 Supervisor: Stephen F. Martin An iminium ion cascade sequence was designed and its implementation attempted to form the pentacyclic core structure of the natural product condylocarpine. Trapping of the transient Pictet-Spengler-type spiroindolenium ion with a latent nucleophile would form two of the five rings of condylocarpine in a regioselective manner. Progress towards the first fully stereocontrolled synthesis of a lysergic acid derivative has been described. The route utilizes intermediates with the appropriate oxidation state for the target, and the two stereocenters are installed via asymmetric catalysis. The d ring and second stereocenter were simultaneously formed via an unprecedented microwave heated asymmetric ring closing metathesis (ARCM). iv Table of Contents List of Figures.....................................................................................................
    [Show full text]
  • Ergometrine Maleate
    The European Agency for the Evaluation of Medicinal Products Veterinary Medicines Evaluation Unit EMEA/MRL/237/97-FINAL June 1999 COMMITTEE FOR VETERINARY MEDICINAL PRODUCTS ERGOMETRINE MALEATE SUMMARY REPORT 1. Ergometrine is a naturally occurring alkaloid found in ergot (Claviceps purpurea). It is classified as a water-soluble lysergic acid derivative, and is an orally-active stimulant of uterine contractions. The maleate salt (ergometrine maleate) exhibits greater stability than the free base and is the usual form in which the alkaloid is used in medicinal products. It is used in veterinary medicine in the control of postpartum uterine haemorrhage, removal of fluid from atonic uteri, to prevent pro-lapsed uteri, and judiciously in terms of timing to aid in suturing the uterus after caesarean section or in replacing an everted uterus. Dose regimens are: cows and mares: 2 to 5 mg/animal (intravenously or intramuscularly); ewes, goats and sows: 0.5 to 1 mg/animal (intramuscularly). In human medicine, it is used orally and parenterally in the prevention and treatment of postpartum haemorrhage caused by uterine atony and for the stimulation of uterine involution. Usual oral doses are 500 µg 3 times daily up to 1.8 mg daily (approximately 0.03 mg/kg bw). Ergot alkaloids have been reported to be present in flour from rye, wheat and barley in amounts ranging from 0.01 to 2.36 mg/kg flour. EU legislation restricts the maximum percentage of ergot tolerated in flour to 0.1%. Total daily human intake of ergot alkaloids from contaminated foodstuffs of plant origin has been estimated as up to 7.8 µg/person.
    [Show full text]
  • Biosynthetic Studies on Ergot Alkaloids and Related Indoles*
    Acla Phartti. Suecica 3, 71 (1966) Biosynthetic studies on ergot alkaloids and related indoles* STiG AGURELL Department of Pharmacognosy, Kungl. Formaceuiislea Instituiei, Stockholm In this survey, the following papers will be discussed and will be referred to by the Roman numerals given in the following list. I. S.Agurcll and E. Ramstad. Analysis of claviric alkaloids of Penniselum ergot. Lloydia 25,67 (1962) II. S. Agurcll. Thin-layer chromatographic and thin-layer electrophoretic analysis of ergot alkaloids. Relations between structure, R" value and electrophoretic mobility in the clavine series. ltcla Pliarm, Suecica 2, 357 (1965) III. S. Agurell and E.Ramstad. Biogenetic interrelationships of ergot alka- loids. Tetrahedron Letters 501 (1961) IV. S. Agurell and E. Ramstad. Biogenetic interrelationships of ergot alka- loids. Arch. Biocliem, Bioplujs. 98, 457 (1962) V. S. Agurell and E. Ramstad. A new ergot alkaloid from Mexican maize ergot. Acta Pliartn, Suecica 2, 231 (1965) VI. S. AgurelJ. Costaclavine from Penicillium chermesinutn, Bxperieniia 20, 25 (1964) VII. S. Agurell. Isol ysergol from saprophytic cultures of ergot. Acta Pliartn, Suecica 3,7 (1966) VIII. S. Agurell and IVI. Johansson. Clavine alkalo ids as precursors of peptide- type ergot alkaloids. Acta Chern. Scand. 18, 2285 (1964) * Inaugural dissertation. 71 IX.S. Agurell.Biosynthesis of ergot alkaloids in C. paspali, Part I. Incor- poration of DL-4-dimethylallyltryptophan-HC. _4cla Pliarm, Suecica 3, 11 (1966) X. S. Agurell. Biosynthesis of ergot alkaloids in C. paspali. Part II. Incor- poration of labelled agroclavine, clymoclavinc, lysergic acid and lysergic acid methyl ester. Acla Pliarm, Suecica 3, 23 (1966) XI. S.Agurell.
    [Show full text]