DOCSLIB.ORG

Addition / C-C Bond Cleavage Reactions of Vinylogous Acyl Triflates and Their Application to Natural Product Synthesis David Mack Jones

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Addition / C-C Bond Cleavage Reactions of Vinylogous Acyl Triflates and Their Application to Natural Product Synthesis David Mack Jones Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2010 Addition / C-C Bond Cleavage Reactions of Vinylogous Acyl Triflates and Their Application to Natural Product Synthesis David Mack Jones Follow this and additional works at the FSU Digital Library. For more information, please contact [email protected] THE FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES ADDITION / C-C BOND CLEAVAGE REACTIONS OF VINYLOGOUS ACYL TRIFLATES AND THEIR APPLICATION TO NATURAL PRODUCT SYNTHESIS By DAVID MACK JONES A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy Degree Awarded: Spring Semester, 2010 Copyright © 2010 David M. Jones All Rights Reserved The members of the committee approve the dissertation of David M. Jones defended on December 3, 2009. __________________________________ Gregory B. Dudley Professor Directing Dissertation __________________________________ Kenneth Taylor University Representative __________________________________ Jack Saltiel Committee Member __________________________________ D. Tyler McQuade Committee Member __________________________________ Kenneth Goldsby Committee Member Approved: _____________________________________ Joseph B. Schlenoff, Chair, Department of Chemistry and Biochemistry The Graduate School has verified and approved the above-named committee members. ii This manuscript is dedicated to my Mother and Father, without whom I would have been lost. Their constant and unwavering support has made all that I am, and all that I will be, possible. iii ACKNOWLEDGEMENTS This body of work has been made possible not only through my hard work, but through the personal and academic support of many people. I would like acknowledge Professor Gregory Dudley. He was charged with the difficult task of not only providing challenging problems for me, his student, to explore, but also he had to provide an environment in which I could hone my own set of tools for future scientific endeavors. As a naïve 1st year graduate student I joined his research group and his constant guidance set me on the right path. As the years progressed he no longer provided answers, but only answered my questions with yet more questions. I remember being completely frustrated at the time with this tact. However now, in the waning moments of my graduate studies, I understand the role that a research advisor must play in the development of a Ph.D. student. I owe much to Dr. Dudley and I am very appreciative of his ability to change me from that naïve graduate student into the independent scientist that I have become today. I would also like to thank the members of the Dudley research group: Dr. Tim Briggs, who introduced me to lab techniques, and guided my early research; Dr. Shin Kamijo, who made my work possible through his early efforts; Dr. Doug Engel, who entered the lab at the same time as I and provided constant competition; Sami Tlais and Jingyue Yang, who often provided company late into the night in the lab; Marilda Lisboa, who provided several intermediates in my palmerolide research; and the rest of the members, past and present. I would like to acknowledge my family for providing constant support, financial and otherwise. Mom and Dad, you have truly been the foundation of my life. Although many times in grad school, you could not offer any advice to help me with my problems, you always made sure that I knew you would do anything in your power to help me. Amy, Laura, Ken, and your families, you have provided support to me in ways that you cannot even understand. I am thankful for your understanding of my inability to attend family gatherings, niece and nephew birthday parties, and other important milestones. Bamp, June, Grammy, and everyone else in the family, thank you. I would like to thank Kerri, a very big part of my life throughout graduate school; you have helped me through many difficult times. I would like to thank the Pritchard family for being like a second family to me. Thanks to Doug, Kerry, Phil, Chris, Antonio, Matt, Mike, Scott and all the other great friends in my life. I wish I had more space to mention all of those people that deserve recognition for supporting me in the generation of this manuscript, please forgive me for any omissions. Lastly, I would like to thank all of those who helped me edit this manuscript, without whom, this document would not have been possible: Kerry Gilmore, Sami Tlais, Marilda Lisboa, and Professor Dudley. iv TABLE OF CONTENTS List of Tables .................................................................................. ….. vi List of Figures ................................................................................. ….. vii List of Abbreviations ....................................................................... ….. xii Abstract .................................................................................... ….. xviii 1. INTRODUCTION: C-C BOND CLEAVAGE AND FRAGMENTATION REACTIONS IN ORGANIC SYNTHESIS........ 1 2. SYNTHESIS OF (Z)-6-HENEICOSEN-11-ONE: THE SEX PHEROMONE OF THE DOUGLAS-FIR TUSSOCK MOTH ..... ….. 13 The Doulas-Fir Tussock Moth ........................................... ….. 13 Synthesis of (Z)-6-Heneicosen-11-one ............................. ….. 16 Experimental ..................................................................... ….. 21 3. A FRAGMENTATION / BENZANNULATION STRATEGY TO PROVIDE ACCESS TO BENZO-FUSED INDANES ................. 37 Introduction ....................................................................... ….. 37 The Alcyopterosins ........................................................... ….. 37 Retrosynthetic Analysis of Alcyopterosin A ....................... ….. 53 Exploring Gold and Copper Catalyzed Benzannulations .. .. 59 Experimental ..................................................................... ….. 70 4. SYNTHESIS OF THE EASTERN HEMISPHERE (C1-C15) OF PALMEROLIDE A ............................................................... ….. 115 Introduction ....................................................................... ….. 115 The Melanoma Problem .................................................... ….. 116 Palmerolide A ................................................................... ….. 121 Synthesis of the Eastern Hemisphere of Palmerolide A ... ….. 138 Experimental ..................................................................... ….. 145 5. RE-EXPLORING THE CLAISEN-TYPE CONDENSATIONS OF VINYLOGOUS ACYL TRIFLATES ...................................... ….. 170 New Insights into the Mechanism ..................................... ….. 170 Synthesis of -Ketophosphonates .................................... ….. 177 Experimental ..................................................................... ….. 184 REFERENCES .............................................................................. ….. 202 BIOGRAPHICAL SKETCH ............................................................. ….. 222 v LIST OF TABLES Table 1: Scope of Original Fragmentation Reaction with Respect to Nucleophiles ............................................................................... 11 Table 2: Grignard Triggered Fragmentation of 2 ....................................... 20 Table 3: DNA Binding Assay Performed by Iglesias et al. ......................... 51 Table 4: Average Values (MG-MID) for In Vitro Antitumor Activity on the NCI 60-Cell Line Panel ................................................................ 52 Table 5: Preliminary Screening of Benzannulation Reactions of Substrates 84a-f.......................................................................... 65 Table 6: Selected Data from Nicolaou’s SAR Study (GI50 Values in M) .. 133 Table 7: Claisen-Type Condensation of Vinylogous Acyl Triflate 2 ........... 141 Table 8: Comparison of the Acidities of Several Acetophenone Phosphonate and Phosphine Oxide Derivatives in DMSO .......... 174 Table 9: Reactions of Vinylogous Acyl Triflates with 1.1 Equivalents of Dimethyl lithiomethylphosphonate (152b) ................................... 180 Table 10: Fragmentation of VAT 2 Using 1.1 Equivalents of Various Phosphonate Derived Nucleophiles .......................................... 182 vi LIST OF FIGURES Figure 1: Representative examples of the (1) Diels-Alder, (2) Michael Addition, (3) Evans Aldol, (4) and Sonogashira Cross Coupling Reactions in Synthesis ............................................................... 2 Figure 2: Examples of Tandem Bond Forming / Bond Breaking Strategies in Organic Synthesis .................................................................. 3 Figure 3: Examples of Transition Metal Catalyzed C-C Bond Cleavage Reactions in Synthesis ............................................................... 4 Figure 4: Possible Mechanistic Pathways of Grob Fragmentations .......... 6 Figure 5: General Representation of the Wharton Fragmentation ............ 6 Figure 6: Wood and Njardarson’s Wharton fragmentation approach to CP-263,114 ................................................................................ 7 Figure 7: Base Promoted Eschenmoser-Tanabe Fragmentation Process. ..................................................................................... 8 Figure 8: Mander’s Reduction-Epoxidation-Oxidation Solution for the Eschenmoser-Tanabe Fragmentation in the Synthesis of GB 13 ......................................................................................... 9 Figure 9: Comparison
Load more

Recommended publications
  • The Alcohol Textbook 4Th Edition
    TTHEHE AALCOHOLLCOHOL TEXTBOOKEXTBOOK T TH 44TH EEDITIONDITION A reference for the beverage, fuel and industrial alcohol industries Edited by KA Jacques, TP Lyons and DR Kelsall Foreword iii The Alcohol Textbook 4th Edition A reference for the beverage, fuel and industrial alcohol industries K.A. Jacques, PhD T.P. Lyons, PhD D.R. Kelsall iv T.P. Lyons Nottingham University Press Manor Farm, Main Street, Thrumpton Nottingham, NG11 0AX, United Kingdom NOTTINGHAM Published by Nottingham University Press (2nd Edition) 1995 Third edition published 1999 Fourth edition published 2003 © Alltech Inc 2003 All rights reserved. No part of this publication may be reproduced in any material form (including photocopying or storing in any medium by electronic means and whether or not transiently or incidentally to some other use of this publication) without the written permission of the copyright holder except in accordance with the provisions of the Copyright, Designs and Patents Act 1988. Applications for the copyright holder’s written permission to reproduce any part of this publication should be addressed to the publishers. ISBN 1-897676-13-1 Page layout and design by Nottingham University Press, Nottingham Printed and bound by Bath Press, Bath, England Foreword v Contents Foreword ix T. Pearse Lyons Presient, Alltech Inc., Nicholasville, Kentucky, USA Ethanol industry today 1 Ethanol around the world: rapid growth in policies, technology and production 1 T. Pearse Lyons Alltech Inc., Nicholasville, Kentucky, USA Raw material handling and processing 2 Grain dry milling and cooking procedures: extracting sugars in preparation for fermentation 9 Dave R. Kelsall and T. Pearse Lyons Alltech Inc., Nicholasville, Kentucky, USA 3 Enzymatic conversion of starch to fermentable sugars 23 Ronan F.
    [Show full text]
  • Production of Arabitol from Glycerol: Strain Screening and Study of Factors Affecting Production Yield
    Appl Microbiol Biotechnol (2011) 90:257–267 DOI 10.1007/s00253-010-3015-3 APPLIED MICROBIAL AND CELL PHYSIOLOGY Production of arabitol from glycerol: strain screening and study of factors affecting production yield Srujana Koganti & Tsung Min Kuo & Cletus P. Kurtzman & Nathan Smith & Lu-Kwang Ju Received: 26 August 2010 /Revised: 10 November 2010 /Accepted: 15 November 2010 /Published online: 3 December 2010 # Springer-Verlag 2010 Abstract Glycerol is a major by-product from biodiesel Keywords Arabitol . Xylitol . Biodiesel . Glycerol . production, and developing new uses for glycerol is Osmotolerant yeast . Debaryomyces hansenii imperative to overall economics and sustainability of the biodiesel industry. With the aim of producing xylitol and/or arabitol as the value-added products from glycerol, 214 Introduction yeast strains, many osmotolerant, were first screened in this study. No strains were found to produce large amounts of Biodiesel motor fuel produced from renewable sources such xylitol as the dominant metabolite. Some produced polyol as vegetable oil and animal fat is an attractive alternative to mixtures that might present difficulties to downstream petroleum-derived fuel (Krawczyk 1996). In biodiesel separation and purification. Several Debaryomyces hansenii production using transesterification of triglycerides, glycerol strains produced arabitol as the predominant metabolite is the major by-product produced: About 1 kg of glycerol is with high yields, and D. hansenii strain SBP-1 (NRRL Y- formed for every 9 kg of biodiesel produced (Dasari et al. 7483) was chosen for further study on the effects of several 2005). Biodiesel consumption in the USA has increased growth conditions. The optimal temperature was found to dramatically from 75 million gallons in 2005 to 450 million be 30°C.
    [Show full text]
  • Approaches Towards the Synthesis of Bradyoxetin
    University of Mississippi eGrove Electronic Theses and Dissertations Graduate School 2010 Approaches Towards the Synthesis of Bradyoxetin Vanildo Martins Lima Braga Follow this and additional works at: https://egrove.olemiss.edu/etd Part of the Organic Chemistry Commons Recommended Citation Braga, Vanildo Martins Lima, "Approaches Towards the Synthesis of Bradyoxetin" (2010). Electronic Theses and Dissertations. 61. https://egrove.olemiss.edu/etd/61 This Dissertation is brought to you for free and open access by the Graduate School at eGrove. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of eGrove. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Vanildo Martins L. Braga entitled “Approaches Towards the Synthesis of Bradyoxetin. ” I have examined the final copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Pharmaceutical Sciences , with an emphasis in Medicinal Chemistry . ______________________________ John M. Rimoldi, Major Professor Professor of Medical Chemistry We have read this dissertation and recommend its acceptance: _____________________________________ Mitchell A. Avery Professor of Medicinal Chemistry _____________________________________ Franck E. Dayan Adjunct Professor of Medicinal Chemistry _____________________________________ Marc Slattery Professor of Pharmacognosy Accepted for the Council: ____________________________ Dean of the Graduate School STATEMENT OF PERMISSION TO USE In presenting this thesis in partial fulfillment of the requirements for a Ph.D. degree at The University of Mississippi, I agree that the Library shall make it available to borrowers under rules of the Library.
    [Show full text]
  • Recyclization Reactions of 8,10-Dibromocamphor with Grignard and Organolithium Compounds Ihor S
    FRENCH-UKRAINIAN JOURNAL OF CHEMISTRY (2021, VOLUME 09, ISSUE 01) Recyclization reactions of 8,10-dibromocamphor with Grignard and organolithium compounds Ihor S. Verenka, Marian V. Gorichko* Department of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska Street, 64/13, Kyiv 01601, Ukraine [email protected] Keywords: camphor, recyclization, Grob fragmentation, intramolecular alkylation, bicyclo[3.2.0]heptane. Grignard reagents and organolithium compounds react with 8,10-dibromocamphor to afford substituted 1-methyl-2-methylenebicyclo[3.2.0]heptanes. Recyclization proceeds via intramolecular enolate alkylation and Grob fragmentation of the reaction intermediates. All compounds have been characterized by 1H, 13C and 19F NMR spectroscopy and their chemical composition proved by HRMS analyses. The relative spatial arrangement of substituents in the molecule of (1-methyl-2- methylenebicyclo[3.2.0]heptan-6-yl)diphenylmethanol was studied by NOESY experiments. ________________________________________________________________________________ Introduction Even nowadays, comparing to other Camphor is known as the naturally relatively simple natural molecules, the available starting material in a number of chemistry of camphor has many uncharted syntheses of more complex compounds from the domains. middle of the XIX century. Nowadays many Electrophilic bromination is the very syntheses of steroids [1-3], terpenoids [4-12], important approach in the preparation of bromo- vitamins [13-15] and other natural products [16- functionalized terpenoid derivatives, which are 19] that involve camphor or its derivatives are common as intermediates in organic synthesis described in the literature. because of the ease of further modifications via Camphor derived chiral auxiliaries can nucleophilic substitutions or various skeletal be prepared in both enantiomeric forms since rearrangements and cyclizations [26–30].
    [Show full text]
  • Microbial Production of Xylitol from D-Arabitol by Gluconobacter Oxydans
    Advances in Biological Sciences Research, volume 3 International Conference on Biological Engineering and Pharmacy (BEP 2016) Microbial Production of Xylitol from D-arabitol by Gluconobacter Oxydans Huanhuan ZHANG Junhua YUN School of Food & Biological Engineering School of Food & Biological Engineering Jiangsu University Jiangsu University Zhenjiang, China Zhenjiang, China e-mail: [email protected] e-mail: [email protected] Tinashe Archbold MAGOCHA Miaomiao YANG School of Food & Biological Engineering School of Food & Biological Engineering Jiangsu University Jiangsu University Zhenjiang, China Zhenjiang, China e-mail: [email protected] e-mail: [email protected] Yanbo XUE Xianghui QI* School of Food & Biological Engineering School of Food & Biological Engineering Jiangsu University Jiangsu University Zhenjiang, China Zhenjiang, China e-mail: [email protected] e-mail: [email protected] Abstract—Xylitol, a five carbon sugar alcohol, has numerous there have no any microbe can transform glucose to xylitol applications in the fields of food and pharmaceuticals. directly in the nature. G.oxydans can produce xylitol from Gluconobacter oxydans contains two enzymes which are D-arabitol based on two simple steps including two key membrane-bound D-arabitol dehydrogenase and soluble enzymes (ArDH and XDH) in the metabolic pathway. This xylitol dehydrogenase enabling the production of xylitol from review introduces the research of xylitol production from D-arabitol. This review provides comprehensive insights D-arabitol by G. oxydan based on the special mechanisms, regarding properties of key enzymes and advances of xylitol and the biotransformation process of D-arablitol to xylitol, production of G. oxydans by microbial methods. and some achievements of microbial production of xylitol from D-arabitol by G.oxydans.
    [Show full text]
  • UNITED STATES PATENT OFFICE 2,128,946 TETRAPHOSPHORCAC) ESTERS Morris B
    - if 3 {: 3 S ; 4 £, A2) g f sub. Patented Sep 8, 1938 2,128,946 care." UNITED STATES PATENT OFFICE 2,128,946 TETRAPHOSPHORCAC) ESTERS Morris B. Katzman, Chicago, Ill. No Drawing. Application April 9, 1937, Serial No. 135,931 23 (Claims. (C. 260-46) My invention relates to a new class of chemi More specifically, the most preferable of the cal substances. It relates more in particular to compounds of my invention may be defined as . a class of chemical, substances having the prop tetraphosphoric acid esters of polyhydroxy sub erties of interface modifiers as, for example, when stances wherein at least one hydroxy group of employed in a treating bath containing textile, the polyhydroxy substance has its hydrogen sub leather or ores. Many of the compounds of my stituted by a lipophile group. The lipophile group 5 invention are also effective to decrease the spat- nay include any organic acid group, particular tering of margarine, to increase the oiliness of ly fatty acid groups having preferably at least lubricating oils and greases, such as are derived four carbon atoms such as the fatty acid radi O from mineral oils, to act as emulsifying agents calls of the following acids: caproic acid, capric, O for cosmetic and other emulsions, to reduce vis- caprylic, valeric, butyric, abietic, naphthenic, hy cosity of chocolate and the like, to retard the droxystearic, benzoic, benzoylbenzoic, naphthoic, rancidification of oils, fats, and vitamin prepara- toluic, higher molecular weight saturated and tions which are subject to deterioration by oxi- unsaturated fatty acids including palmitic acid, dation, to act as assistants in the textile and re- Stearic, lauric, melissic, oleic, myristic, ricinoleic, 5 5 lated industries and, in general, to function linoleic acid or mixed fatty acids derived from wherever interface modification is sought or de- animal or vegetable fats and fish oils such as sired.
    [Show full text]
  • Sugar Alcohols a Sugar Alcohol Is a Kind of Alcohol Prepared from Sugars
    Sweeteners, Good, Bad, or Something even Worse. (Part 8) These are Low calorie sweeteners - not non-calorie sweeteners Sugar Alcohols A sugar alcohol is a kind of alcohol prepared from sugars. These organic compounds are a class of polyols, also called polyhydric alcohol, polyalcohol, or glycitol. They are white, water-soluble solids that occur naturally and are used widely in the food industry as thickeners and sweeteners. In commercial foodstuffs, sugar alcohols are commonly used in place of table sugar (sucrose), often in combination with high intensity artificial sweeteners to counter the low sweetness of the sugar alcohols. Unlike sugars, sugar alcohols do not contribute to the formation of tooth cavities. Common Sugar Alcohols Arabitol, Erythritol, Ethylene glycol, Fucitol, Galactitol, Glycerol, Hydrogenated Starch – Hydrolysate (HSH), Iditol, Inositol, Isomalt, Lactitol, Maltitol, Maltotetraitol, Maltotriitol, Mannitol, Methanol, Polyglycitol, Polydextrose, Ribitol, Sorbitol, Threitol, Volemitol, Xylitol, Of these, xylitol is perhaps the most popular due to its similarity to sucrose in visual appearance and sweetness. Sugar alcohols do not contribute to tooth decay. However, consumption of sugar alcohols does affect blood sugar levels, although less than that of "regular" sugar (sucrose). Sugar alcohols may also cause bloating and diarrhea when consumed in excessive amounts. Erythritol Also labeled as: Sugar alcohol Zerose ZSweet Erythritol is a sugar alcohol (or polyol) that has been approved for use as a food additive in the United States and throughout much of the world. It was discovered in 1848 by British chemist John Stenhouse. It occurs naturally in some fruits and fermented foods. At the industrial level, it is produced from glucose by fermentation with a yeast, Moniliella pollinis.
    [Show full text]
  • UNITED STATES PATENT OFFICE 2,530,872 ESTERS 0F SULFUR-CONTAINING POLYCARBOXYLIC ACIDS James T
    Patented Nov. 21, 1950 2,530,872 UNITED STATES PATENT OFFICE 2,530,872 ESTERS 0F SULFUR-CONTAINING POLYCARBOXYLIC ACIDS James T. Gregory, Cuyahoga Falls, and Jacob Eden Jansen, Akron, Ohio, assignors to The B. F. Goodrich Company, New York, N. Y., a corporation of New York No Drawing. Application June 18, 1947, Serial No. 755,478 3 Claims. (Cl. 260—30.8) 2 This invention relates to new compositions of primary, secondary, or tertiary mono- or poly matter, and pertains more speci?cally to new hydroxy, substituted or unsubstituted alcohol. esters of sulfur-containing polycarboxylic acids. Among these are: primary alkyl alcohols such as It is disclosed in our copending application, Se methyl alcohol, ethyl alcohol, propyl alcohol, bu rial No. 755,476, ?led June 17, 1947, that new acids tyl alcohol, amyl alcohol, hexyl alcohol, heptyl al having the general formula cohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tetradecyl alco hol, cetyl alcohol, octadecyl alcohol, and the like; Secondary alkyl alcohols such as isopropyl al wherein A is a polyvalent aliphatic radical hav ll) cohol, secondary butyl alcohol, secondary amyl ing its connecting valences on carbon atoms and alcohol, secondary hexyl alcohol, secondary octyl containing only atoms of carbon, hydrogen and alcohol, secondary nonyl alcohol and the like; sulfur or oxygen (1. e., a chalcogen occurring in Tertiary alkyl alcohols such as tertiary butyl one of the short periods of the periodic table), the alcohol, tertiary amyl alcohol, tertiary butyl car sulfur or oxygen being present in the divalent 15 bino, tertiary amyl carbinol, pinacoylyl alcohol.
    [Show full text]
  • 1 the Principle of Conservation of Structural Aspect: Facilitating Visual Communication and Learning in Organic Chemistry Instr
    1 The Principle of Conservation of Structural Aspect: Facilitating Visual Communication and Learning in Organic Chemistry Instruction John Andraos CareerChem 504-1129 Don Mills Road Toronto, ON M3B 2W4 Canada [email protected] Abstract An effective pedagogical method is presented for the visual communication of chemical reactions learned in organic chemistry undergraduate courses. The basis for the method is the preservation of the visual aspect of reactant and product structures so that the tracking of cleaved and formed chemical bonds is made self-evident. This consequently leads to improved clarity of presentation and a better understanding and grasp of proposed reaction mechanisms to explain product outcomes. The method is demonstrated for a variety of individual reaction types and synthesis plans. Various visual training exercises are also presented using ChemDraw Ultra 7.0 software and literature table of contents (TOC) graphics appearing in journal articles. Keywords: upper-division undergraduate, curriculum, organic chemistry pedagogy, problem solving, organic synthesis Introduction It is well known that when students encounter organic chemistry for the first time in undergraduate courses, they perceive the subject as “hard”. From their point of view their complaint stems from two major issues: (a) the apparent overwhelming volume of material that needs to be digested and learned in a relatively short period of time 2 (typically a three-month course session); and (b) the material is presented in a visual manner that is not always “easy” or evident to understand what is going in any given chemical reaction that is presented to them. The inevitable outcome is increased frustration and ultimately a dislike for the subject for the majority of students, particularly those that take organic chemistry as a standard mandatory requirement for other disciplines such as pre-medical studies and life sciences.
    [Show full text]
  • Terpene and Terpenoid Emissions and Secondary Organic Aerosol Production
    Michigan Technological University Digital Commons @ Michigan Tech Dissertations, Master's Theses and Master's Dissertations, Master's Theses and Master's Reports - Open Reports 2013 TERPENE AND TERPENOID EMISSIONS AND SECONDARY ORGANIC AEROSOL PRODUCTION Rosa M. Flores Michigan Technological University Follow this and additional works at: https://digitalcommons.mtu.edu/etds Part of the Atmospheric Sciences Commons, and the Environmental Engineering Commons Copyright 2013 Rosa M. Flores Recommended Citation Flores, Rosa M., "TERPENE AND TERPENOID EMISSIONS AND SECONDARY ORGANIC AEROSOL PRODUCTION", Dissertation, Michigan Technological University, 2013. https://doi.org/10.37099/mtu.dc.etds/818 Follow this and additional works at: https://digitalcommons.mtu.edu/etds Part of the Atmospheric Sciences Commons, and the Environmental Engineering Commons TERPENE AND TERPENOID EMISSIONS AND SECONDARY ORGANIC AEROSOL PRODUCTION By Rosa M. Flores A DISSERTATION Submitted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY In Environmental Engineering MICHIGAN TECHNOLOGICAL UNIVERSITY 2013 © Rosa M. Flores This dissertation has been approved in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY in Environmental Engineering. Department of Civil and Environmental Engineering Dissertation Advisor: Paul V. Doskey Committee Member : Chandrashekhar P. Joshi Committee Member : Claudio Mazzoleni Committee Member : Lynn Mazzoleni Committee Member : Judith Perlinger Department Chair: David Hand To dad
    [Show full text]
  • Arabitol Dehydrogenase As a Selectable Marker for Rice
    Plant Cell Rep (2005) 24: 596–602 DOI 10.1007/s00299-005-0015-3 GENETIC TRANSFORMATION AND HYBRIDIZATION P. R. LaFayette · P. M. Kane · B. H. Phan · W. A. Parrott Arabitol dehydrogenase as a selectable marker for rice Received: 22 December 2004 / Revised: 15 April 2005 / Accepted: 11 May 2005 / Published online: 8 September 2005 C Springer-Verlag 2005 Abstract Arabitol dehydrogenase has been adapted for use both positive and negative selection is possible, depending as a plant selectable marker. Arabitol is a five-carbon sugar on the substrate employed (Erikson et al. 2004). alcohol that can be used by E. coli strain C, but not by Negative selection kills the cells which do not contain the the laboratory K12 strains. The enzyme converts the non- introduced DNA, and includes antibiotic- and herbicide- plant-metabolizable sugar arabitol into xylulose, which is based selection. Plant cells dying from antibiotic toxicity metabolized by plant cells. Rice was transformed with a release growth inhibitors and toxins which are thought to plant-expression-optimized synthetic gene using Biolistic- negatively affect transformed cells and hinder their growth mediated transformation. Selection on 2.75% arabitol and (Haldrup et al. 1998a), thus limiting the transformation 0.25% sucrose yielded a transformation efficiency (9.3%) efficiency of negative systems. The commonly used equal to that obtained with hygromycin (9.2%). Molecular antibiotic selective agents, kanamycin and hygromycin, analyses showed that the atlD gene was integrated into cause genome-wide alterations in DNA methylation the rice genome of selected plants and was inherited in a (Schmitt et al. 1997).
    [Show full text]
  • Production of Some Higher Alcohols and Acetate Esters from Rice Bran by Yeasts Metabolisms of Kluyveromyces Marxianus and Debaryomyces Hansenii
    Production of Some Higher Alcohols and Acetate Esters from Rice Bran by Yeasts Metabolisms of Kluyveromyces Marxianus and Debaryomyces Hansenii Onur Güneşer Uşak Üniversitesi: Usak Universitesi https://orcid.org/0000-0002-3927-4469 Y. Karagul Yuceer ( [email protected] ) ÇOMÜ: Canakkale Onsekiz Mart Universitesi https://orcid.org/0000-0002-9028-2923 Müge İşleten Hoşoğlu Gebze Institute of Technology: Gebze Teknik Universitesi https://orcid.org/0000-0001-8171-3018 Sine Özmen Toğay Bursa Uludağ Üniversitesi: Bursa Uludag Universitesi https://orcid.org/0000-0002-8851-1803 Murat Elibol Ege University: Ege Universitesi https://orcid.org/0000-0002-6756-6290 Research Article Keywords: Bioavor, microbial fermentation, yeast metabolism, Gas chromatography olfactometry, sensory analysis Posted Date: February 16th, 2021 DOI: https://doi.org/10.21203/rs.3.rs-198090/v1 License: This work is licensed under a Creative Commons Attribution 4.0 International License. Read Full License Page 1/19 Abstract The aim of this study was to evaluate the biosynthesis of avor compounds from rice bran by yeast metabolisms. The microbial growth and avor biosynthesis of Kluyveromyces marxianus and Debaryomyces hansenii in rice bran by microbial fermentation were investigated. Growth of both yeasts was assessed by the calculation of specic growth rates and doubling time. Their aroma biosynthesis was evaluated by gas chromatography-olfactometry (GC-O), gas chromatography-mass spectrometry (GC-MS) and Spectrum™ sensory analysis. The specic growth rate (µmax) and doubling time (td) of K. marxianus were calculated as 0.16/h and 4.21 h respectively, D. hansenii had 0.13/h of µmax and 5.33h of td.
    [Show full text]