DOCSLIB.ORG

Che 333 Organic Chemistry Iii

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

OIT: CHE 333 ORGANIC CHEMISTRY III Travis Lund Oregon Institute of Technology Oregon Institute of Technology OIT: CHE 333 Organic Chemistry III Travis Lund This text is disseminated via the Open Education Resource (OER) LibreTexts Project (https://LibreTexts.org) and like the hundreds of other texts available within this powerful platform, it freely available for reading, printing and "consuming." Most, but not all, pages in the library have licenses that may allow individuals to make changes, save, and print this book. Carefully consult the applicable license(s) before pursuing such effects. Instructors can adopt existing LibreTexts texts or Remix them to quickly build course-specific resources to meet the needs of their students. Unlike traditional textbooks, LibreTexts’ web based origins allow powerful integration of advanced features and new technologies to support learning. The LibreTexts mission is to unite students, faculty and scholars in a cooperative effort to develop an easy-to-use online platform for the construction, customization, and dissemination of OER content to reduce the burdens of unreasonable textbook costs to our students and society. The LibreTexts project is a multi-institutional collaborative venture to develop the next generation of open-access texts to improve postsecondary education at all levels of higher learning by developing an Open Access Resource environment. The project currently consists of 13 independently operating and interconnected libraries that are constantly being optimized by students, faculty, and outside experts to supplant conventional paper-based books. These free textbook alternatives are organized within a central environment that is both vertically (from advance to basic level) and horizontally (across different fields) integrated. The LibreTexts libraries are Powered by MindTouch® and are supported by the Department of Education Open Textbook Pilot Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions Program, and Merlot. This material is based upon work supported by the National Science Foundation under Grant No. 1246120, 1525057, and 1413739. Unless otherwise noted, LibreTexts content is licensed by CC BY-NC-SA 3.0. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation nor the US Department of Education. Have questions or comments? For information about adoptions or adaptions contact [email protected]. More information on our activities can be found via Facebook (https://facebook.com/Libretexts), Twitter (https://twitter.com/libretexts), or our blog (http://Blog.Libretexts.org). This text was compiled on 09/26/2021 TABLE OF CONTENTS 1: REACTIONS AT THE Α-CARBON, PART II 1.1: PRELUDE TO REACTIONS AT THE Α-CARBON, PART II 1.2: DECARBOXYLATION 1.3: AN OVERVIEW OF FATTY ACID METABOLISM 1.4: CLAISEN CONDENSATION 1.5: CONJUGATE ADDITION AND ELIMINATION 1.6: CARBOXYLATION 1.7: REACTIONS AT THE Α-CARBON, PART II (EXERCISES) 1.8: REACTIONS AT THE Α-CARBON, PART II (SUMMARY) 2: RETROSYNTHETIC ANALYSIS AND METABOLIC PATHWAY PREDICTION 2.1: PATHWAY PREDICTION PRACTICE PROBLEMS 3: ELECTROPHILIC REACTIONS 3.1: PRELUDE TO ELECTROPHILIC REACTIONS 3.2: ELECTROPHILIC ADDITION TO ALKENES 3.3: ELIMINATION BY THE E1 MECHANISM 3.4: ELECTROPHILIC ISOMERIZATION 3.5: ELECTROPHILIC SUBSTITUTION 3.6: CARBOCATION REARRANGEMENTS 3.7: ELECTROPHILIC REACTIONS (EXERCISES) 3.8: ELECTROPHILIC REACTIONS (SUMMARY) 4: OXIDATION AND REDUCTION REACTIONS 4.1: PRELUDE TO OXIDATION AND REDUCTION REACTIONS 4.2: OXIDATION AND REDUCTION OF ORGANIC COMPOUNDS - AN OVERVIEW 4.3: OXIDATION AND REDUCTION IN THE CONTEXT OF METABOLISM 4.4: HYDROGENATION OF CARBONYL AND IMINE GROUPS 4.5: HYDROGENATION OF ALKENES AND DEHYDROGENATION OF ALKANES 4.6: MONITORING HYDROGENATION AND DEHYDROGENATION REACTIONS BY UV SPECTROSCOPY 4.7: REDOX REACTIONS OF THIOLS AND DISULFIDES 4.8: FLAVIN-DEPENDENT MONOOXYGENASE REACTIONS - HYDROXYLATION, EPOXIDATION, AND THE BAEYER-VILLIGER OXIDATION 4.9: HYDROGEN PEROXIDE IS A HARMFUL - REACTIVE OXYGEN SPECIES 4.10: OXIDATION AND REDUCTION REACTIONS (EXERCISES) 4.11: OXIDATION AND REDUCTION REACTIONS (SUMMARY) 5: RADICAL REACTIONS 5.1: PRELUDE TO RADICAL REACTIONS 5.2: OVERVIEW OF SINGLE-ELECTRON REACTIONS AND FREE RADICALS 5.3: RADICAL CHAIN REACTIONS 5.4: USEFUL POLYMERS FORMED BY RADICAL CHAIN REACTIONS 5.5: DESTRUCTION OF THE OZONE LAYER BY A RADICAL CHAIN REACTION 5.6: OXIDATIVE DAMAGE TO CELLS, VITAMIN C, AND SCURVY 5.7: FLAVIN AS A ONE-ELECTRON CARRIER 5.8: RADICAL REACTIONS (EXERCISES) 5.9: RADICAL REACTIONS (SUMMARY) 6: THE ORGANIC CHEMISTRY OF VITAMINS 6.1: PRELUDE TO THE ORGANIC CHEMISTRY OF VITAMINS 6.2: PYRIDOXAL PHOSPHATE (VITAMIN B6) 6.3: THIAMINE DIPHOSPHATE (VITAMIN B1) 1 9/26/2021 6.4: THIAMINE DIPHOSPHATE, LIPOAMIDE AND THE PYRUVATE DEHYDROGENASE REACTION 6.5: FOLATE 6.6: THE OGANIC CHEMISTRY OF VITAMINS (EXERCISES) 6.7: THE OGANIC CHEMISTRY OF VITAMINS (SUMMARY) 7: INDEX OF ENZYMATIC REACTIONS BY PATHWAY 7.1: AMINO ACID BIOSYNTHESIS 7.2: AMINO ACID CATABOLISM 7.3: CITRIC ACID CYCLE 7.4: FATTY ACID METABOLISM 7.5: GLYCOLYSIS, GLUCONEOGENESIS, FERMENTATION 7.6: ISOPRENOID BIOSYNTHESIS 7.7: NUCLEOSIDE BIOSYNTHESIS 7.8: NUCLEOTIDE CATABOLISM 7.9: PENTOSE PHOSPHATE PATHWAY, CALVIN CYCLE 8: INDEX OF LABORATORY SYNTHESIS REACTIONS BACK MATTER INDEX GLOSSARY 2 9/26/2021 CHAPTER OVERVIEW 1: REACTIONS AT THE Α-CARBON, PART II 1.1: PRELUDE TO REACTIONS AT THE Α-CARBON, PART II 1.2: DECARBOXYLATION 1.3: AN OVERVIEW OF FATTY ACID METABOLISM 1.4: CLAISEN CONDENSATION 1.5: CONJUGATE ADDITION AND ELIMINATION 1.6: CARBOXYLATION 1.7: REACTIONS AT THE Α-CARBON, PART II (EXERCISES) 1.8: REACTIONS AT THE Α-CARBON, PART II (SUMMARY) 1 9/26/2021 1.1: Prelude to Reactions at the α-Carbon, Part II Introduction We begin this chapter with the story of two men, and two chemical reactions. The two men couldn't be more different. One was an acclaimed scientist who lived and continued to work productively into his eighties. The other was struck down as a young boy by what was assumed at the time to be a fatal disease. With the heroic support of his parents and caregivers, though, he lived to his thirtieth birthday and provided the inspiration for development of a medical treatment that could potentially save thousands of lives. The two chemical reactions in this story are closely related, and both involve the metabolism of fats in the human body. One serves to build up fatty acid chains by repeatedly linking together two-carbon units, while the other does the reverse, progressively breaking off two-carbon pieces from a long chain fatty acid molecule. The life and work of the two men are inextricably linked to the two reactions, and while we will be learning all about the reactions in the main part of this chapter, we'll begin with the stories of the two men. On a Saturday in January of 2007, Dr. Hugo Moser passed away in the Johns Hopkins Hospital in Baltimore, succumbing to pancreatic cancer. He was 82 years old. A neurologist who had taught and researched for much of his career at Johns Hopkins, he was well known for his workaholic nature: he had signed off on his last grant application while on the way to the hospital for major surgery just a few months previously. Two days after his death, his wife and colleague Ann Moser was back in their lab, because, she said, “He gave us all a mandate to continue with the work”. Dr. Moser was a highly esteemed scientist who had devoted his life to understanding and eventually curing a class of devastating neurodegenerative diseases, most notably adrenoleukodystrophy, or ALD. In his work he was careful, rational, painstaking, and relentless – a classic scientist. But in the minds of many movie fans, he became a Hollywood villain. Only 17 months after the death of Dr. Moser, newspapers around the world published moving obituaries marking the passing, at age 30, of Lorenzo Odone. In one, written by his older sister and published in the British newspaper The Guardian, Lorenzo as a young boy is described as “lively and charming . .he displayed a precocious gift for languages as he mastered English, Italian and French. He was funny, articulate and favored opera over nursery rhymes.” But for more than 20 years leading up to his death, he had been confined to a wheelchair, blind, paralyzed, and unable to communicate except by blinking his eyes. Because he was unable to swallow, he needed an attendant to be with him around the clock to suction saliva from his mouth so he wouldn't choke. When he was he six years old, Lorenzo started to show changes in behavior: a shortening attention span, moodiness. More disturbing to his parents, Augusto and Michaela Odone, was their suspicion that he was having trouble hearing. They took him in to be examined, and although his hearing was fine, the doctors noticed other behavioral symptoms that concerned them, and so ordered more neurological tests. The results were a kick to the stomach: Lorenzo had a fatal neurodegenerative disease called adrenoleukodystrophy. There was no cure; his nervous system would continue to degenerate, and he would probably be dead within two years. Tim Soderberg 1.1.1 9/19/2021 https://chem.libretexts.org/@go/page/151244 What happened next became such a compelling story that it was eventually retold by director George Miller in the 1992 movie Lorenzo's Oil, starring Nick Nolte and Susan Sarandon as Augusto and Michaela Odone and Peter Ustinov as a character based on Dr. Hugo Moser. The Odones were unwilling to accept the death sentence for their son and, despite having no scientific or medical training, set about to learn everything they could about ALD. They found out that the cause of ALD is a mutation in a gene that plays an important role in the process by which saturated fatty acids of 26 or more carbons are broken down in the body.
Recommended publications
  • A New Insight Into Role of Phosphoketolase Pathway in Synechocystis Sp

    A New Insight Into Role of Phosphoketolase Pathway in Synechocystis Sp

    www.nature.com/scientificreports OPEN A new insight into role of phosphoketolase pathway in Synechocystis sp. PCC 6803 Anushree Bachhar & Jiri Jablonsky* Phosphoketolase (PKET) pathway is predominant in cyanobacteria (around 98%) but current opinion is that it is virtually inactive under autotrophic ambient CO2 condition (AC-auto). This creates an evolutionary paradox due to the existence of PKET pathway in obligatory photoautotrophs. We aim to answer the paradox with the aid of bioinformatic analysis along with metabolic, transcriptomic, fuxomic and mutant data integrated into a multi-level kinetic model. We discussed the problems linked to neglected isozyme, pket2 (sll0529) and inconsistencies towards the explanation of residual fux via PKET pathway in the case of silenced pket1 (slr0453) in Synechocystis sp. PCC 6803. Our in silico analysis showed: (1) 17% fux reduction via RuBisCO for Δpket1 under AC-auto, (2) 11.2–14.3% growth decrease for Δpket2 in turbulent AC-auto, and (3) fux via PKET pathway reaching up to 252% of the fux via phosphoglycerate mutase under AC-auto. All results imply that PKET pathway plays a crucial role under AC-auto by mitigating the decarboxylation occurring in OPP pathway and conversion of pyruvate to acetyl CoA linked to EMP glycolysis under the carbon scarce environment. Finally, our model predicted that PKETs have low afnity to S7P as a substrate. Metabolic engineering of cyanobacteria provides many options for producing valuable compounds, e.g., acetone from Synechococcus elongatus PCC 79421 and butanol from Synechocystis sp. strain PCC 68032. However, certain metabolites or overproduction of intermediates can be lethal. Tere is also a possibility that required mutation(s) might be unstable or the target bacterium may even be able to maintain the fux distribution for optimal growth balance due to redundancies in the metabolic network, such as alternative pathways.
  • Natural Sources, Pharmacokinetics, Biological Activities and Health Benefits of Hydroxycinnamic Acids and Their Metabolites

    Natural Sources, Pharmacokinetics, Biological Activities and Health Benefits of Hydroxycinnamic Acids and Their Metabolites

    nutrients Review Natural Sources, Pharmacokinetics, Biological Activities and Health Benefits of Hydroxycinnamic Acids and Their Metabolites Matej Sova 1,* and Luciano Saso 2 1 Faculty of Pharmacy, University of Ljubljana, Aškerˇceva7, 1000 Ljubljana, Slovenia 2 Department of Physiology and Pharmacology "Vittorio Erspamer", Sapienza University of Rome, Piazzale Aldo Moro 5, 00185 Rome, Italy; [email protected] * Correspondence: matej.sova@ffa.uni-lj.si; Tel.: +386-1-476-9556 Received: 24 June 2020; Accepted: 22 July 2020; Published: 23 July 2020 Abstract: Hydroxycinnamic acids (HCAs) are important natural phenolic compounds present in high concentrations in fruits, vegetables, cereals, coffee, tea and wine. Many health beneficial effects have been acknowledged in food products rich in HCAs; however, food processing, dietary intake, bioaccessibility and pharmacokinetics have a high impact on HCAs to reach the target tissue in order to exert their biological activities. In particular, metabolism is of high importance since HCAs’ metabolites could either lose the activity or be even more potent compared to the parent compounds. In this review, natural sources and pharmacokinetic properties of HCAs and their esters are presented and discussed. The main focus is on their metabolism along with biological activities and health benefits. Special emphasis is given on specific effects of HCAs’ metabolites in comparison with their parent compounds. Keywords: diet; natural compounds; phenolic acids; hydroxycinnamic acids; metabolites; pharmacokinetic properties; biological activities; health effects 1. Introduction Our diet rich in plant food contains several health-beneficial ingredients. Among such ingredients, polyphenols represent one of the most important natural compounds. Phenolic compounds are members of probably the largest group of plant secondary metabolites and have the main function to protect the plants against ultraviolet radiation or invasion by pathogens [1,2].
  • Sterile Spikelets Assimilate Carbon in Sorghum and Related Grasses

    Sterile Spikelets Assimilate Carbon in Sorghum and Related Grasses

    bioRxiv preprint doi: https://doi.org/10.1101/396473; this version posted January 5, 2019. The copyright holder for this preprint (which was not certified by peer review) is the author/funder. This article is a US Government work. It is not subject to copyright under 17 USC 105 and is also made available for use under a CC0 license. 1 Sterile spikelets assimilate carbon in sorghum and related grasses Taylor AuBuchon-Elder1,a, Viktoriya Coneva1,a,d, David M. Goad a,b, Doug K. Allen2,a,c,e, and Elizabeth A. Kellogg2,a,e aDonald Danforth Plant Science Center, St. Louis, Missouri, 63132 USA bDepartment of Biology, Washington University, St. Louis, Missouri, 63130 USA cUSDA-ARS, St. Louis, Missouri, 63132 USA 1These authors contributed equally to this work. 2These authors contributed equally to this work. dCurrent address: Kenyon College, Gambier, OH 43022 eAddress correspondence to: [email protected]; [email protected] ORCID IDs: 0000-0002-0640-5135 (V.C.); 0000-0001-8658-6660 (D.M.G.); 0000-0001-8599- 8946 (D.K.A.); 0000-0003-1671-7447 (E.A.K.) Short title: Carbon assimilation in sorghum spikelets The author responsible for distribution of materials integral to the findings presented in this article is Elizabeth A. Kellogg ([email protected]). bioRxiv preprint doi: https://doi.org/10.1101/396473; this version posted January 5, 2019. The copyright holder for this preprint (which was not certified by peer review) is the author/funder. This article is a US Government work. It is not subject to copyright under 17 USC 105 and is also made available for use under a CC0 license.
  • RESPIRATION Pentose Phosphate Pathway Or Hexose Monophosphate Pathway

    RESPIRATION Pentose Phosphate Pathway Or Hexose Monophosphate Pathway

    RESPIRATION Pentose Phosphate Pathway or Hexose Monophosphate Pathway Pentose phosphate pathway or hexose monophosphate pathway (HMP pathway) is the other common pathway to break down glucose to pyruvate and operates in both aerobic and anaerobic conditions. This pathway produces NADPH, which carries chemical energy in the form of reducing power and is used almost universally as the reductant in anabolic (energy utilization) pathways (e.g., fatty acid biosynthesis, cholesterol biosynthesis, nucleotide biosynthesis) and detoxification pathways (e.g., reduction of oxidized glutathione, cytochrome P450 monooxygenases). Also, the pentose phosphate pathway generates pentose sugar ribose and its derivatives, which are necessary for the biosynthesis of nucleic acids (DNA and RNA) as well as ATP, NADH, FAD, and coenzyme A. In this way, though the pentose phosphate pathway may be a source of energy in many microorganisms, it is more often of greater importance in various biosynthetic pathways. Pentose phosphate pathway consists of two phases: the oxidative phase and the non-oxidative phase. Oxidative Phase: The oxidative phase of the pentose phosphate pathway initiates with the conversion of glucose 6- phosphate to 6-Phosphogluconate. NADP+ is the electron acceptor yielding NADPH during this reaction. 6-Phosphogluconate, a six-carbon sugar, is then oxidativelydecarboxylated to yield ribulose 5-phosphate, a five-carbon sugar. NADP+ is again the electron acceptor yielding NADPH. In the final step of oxidative phase, there is isomerisation of ribulose 5-phosphatc to ribose 5- phosphate by phosphopentose isomerase and the conversion of ribulose 5-phosphate into its epimerxylulose 5-phosphate by phosphopentose epimerase for the transketolase reaction in non- oxidative phase.
  • Dose-Dependent Increase in Unconjugated Cinnamic Acid Concentration in Plasma Following Acute Consumption of Polyphenol Rich Curry in the Polyspice Study

    Dose-Dependent Increase in Unconjugated Cinnamic Acid Concentration in Plasma Following Acute Consumption of Polyphenol Rich Curry in the Polyspice Study

    nutrients Article Dose-Dependent Increase in Unconjugated Cinnamic Acid Concentration in Plasma Following Acute Consumption of Polyphenol Rich Curry in the Polyspice Study Sumanto Haldar 1,† ID , Sze Han Lee 2,† ID , Jun Jie Tan 2, Siok Ching Chia 1, Christiani Jeyakumar Henry 1,3,* ID and Eric Chun Yong Chan 1,2,* 1 Clinical Nutrition Research Centre, Agency for Science, Technology and Research, Singapore Institute for Clinical Sciences, Singapore 117599, Singapore; [email protected] (S.H.); [email protected] (S.C.C.) 2 Department of Pharmacy, National University of Singapore, Singapore 117543, Singapore; [email protected] (S.H.L.); [email protected] (J.J.T.) 3 Department of Biochemistry, National University of Singapore, Singapore 117596, Singapore * Correspondence: [email protected] (C.J.H.); [email protected] (E.C.Y.C.); Tel.: +65-6407-0793 (C.J.H.); +65-6516-6137 (E.C.Y.C.) † Contributed equally to this work. Received: 25 June 2018; Accepted: 18 July 2018; Published: 20 July 2018 Abstract: Spices that are rich in polyphenols are metabolized to a convergent group of phenolic/aromatic acids. We conducted a dose-exposure nutrikinetic study to investigate associations between mixed spices intake and plasma concentrations of selected, unconjugated phenolic/aromatic acids. In a randomized crossover study, 17 Chinese males consumed a curry meal containing 0 g, 6 g, and 12 g of mixed spices. Postprandial blood was drawn up to 7 h at regular intervals and plasma phenolic/aromatic acids were quantified via liquid chromatography tandem mass spectrometry (LC-MS/MS).
  • Journal of Pharmaceutical and Biomedical Analysis 83 (2013) 108–121

    Journal of Pharmaceutical and Biomedical Analysis 83 (2013) 108–121

    Journal of Pharmaceutical and Biomedical Analysis 83 (2013) 108–121 Contents lists available at SciVerse ScienceDirect Journal of Pharmaceutical and Biomedical Analysis jou rnal homepage: www.elsevier.com/locate/jpba The profiling and identification of the absorbed constituents and metabolites of Paeoniae Radix Rubra decoction in rat plasma and urine by the n HPLC–DAD–ESI-IT-TOF-MS technique: A novel strategy for the systematic screening and identification of absorbed constituents and metabolites from traditional Chinese medicines 1 1 Jing Liang , Feng Xu , Ya-Zhou Zhang, Shuai Huang, Xin-Yu Zang, Xin Zhao, Lei Zhang, ∗ Ming-Ying Shang, Dong-Hui Yang, Xuan Wang, Shao-Qing Cai State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, No. 38 Xueyuan Road, Beijing 100191, China a r t i c l e i n f o a b s t r a c t Article history: Paeoniae Radix Rubra (PRR, the dried roots of Paeonia lactiflora) is a commonly used traditional Chinese Received 23 January 2013 medicine (TCM). A clear understanding of the absorption and metabolism of TCMs is very important Received in revised form 13 April 2013 in their rational clinical use and pharmacological research. To find more of the absorbed constituents Accepted 16 April 2013 and metabolites of TCMs, a novel strategy was proposed. This strategy was characterized by the fol- Available online 9 May 2013 lowing: the establishment and utilization of the databases of parent compounds, known metabolites and characteristic neutral losses; the comparison of base peak chromatograms and ClogPs; and the use Keywords: n of the HPLC–DAD–ESI-IT-TOF-MS technique.
  • Studies on Betalain Phytochemistry by Means of Ion-Pair Countercurrent Chromatography

    Studies on Betalain Phytochemistry by Means of Ion-Pair Countercurrent Chromatography

    STUDIES ON BETALAIN PHYTOCHEMISTRY BY MEANS OF ION-PAIR COUNTERCURRENT CHROMATOGRAPHY Von der Fakultät für Lebenswissenschaften der Technischen Universität Carolo-Wilhelmina zu Braunschweig zur Erlangung des Grades einer Doktorin der Naturwissenschaften (Dr. rer. nat.) genehmigte D i s s e r t a t i o n von Thu Tran Thi Minh aus Vietnam 1. Referent: Prof. Dr. Peter Winterhalter 2. Referent: apl. Prof. Dr. Ulrich Engelhardt eingereicht am: 28.02.2018 mündliche Prüfung (Disputation) am: 28.05.2018 Druckjahr 2018 Vorveröffentlichungen der Dissertation Teilergebnisse aus dieser Arbeit wurden mit Genehmigung der Fakultät für Lebenswissenschaften, vertreten durch den Mentor der Arbeit, in folgenden Beiträgen vorab veröffentlicht: Tagungsbeiträge T. Tran, G. Jerz, T.E. Moussa-Ayoub, S.K.EI-Samahy, S. Rohn und P. Winterhalter: Metabolite screening and fractionation of betalains and flavonoids from Opuntia stricta var. dillenii by means of High Performance Countercurrent chromatography (HPCCC) and sequential off-line injection to ESI-MS/MS. (Poster) 44. Deutscher Lebensmittelchemikertag, Karlsruhe (2015). Thu Minh Thi Tran, Tamer E. Moussa-Ayoub, Salah K. El-Samahy, Sascha Rohn, Peter Winterhalter und Gerold Jerz: Metabolite profile of betalains and flavonoids from Opuntia stricta var. dilleni by HPCCC and offline ESI-MS/MS. (Poster) 9. Countercurrent Chromatography Conference, Chicago (2016). Thu Tran Thi Minh, Binh Nguyen, Peter Winterhalter und Gerold Jerz: Recovery of the betacyanin celosianin II and flavonoid glycosides from Atriplex hortensis var. rubra by HPCCC and off-line ESI-MS/MS monitoring. (Poster) 9. Countercurrent Chromatography Conference, Chicago (2016). ACKNOWLEDGEMENT This PhD would not be done without the supports of my mentor, my supervisor and my family.
  • Chapter 23 Gluconeogenesis Gluconeogenesis, Con't

    Chapter 23 Gluconeogenesis Gluconeogenesis, Con't

    BCH 4054 Spring 2001 Chapter 23 Lecture Notes Slide 1 Chapter 23 Gluconeogenesis Glycogen Metabolism Pentose Phosphate Pathway Slide 2 Gluconeogenesis • Humans use about 160 g of glucose per day, about 75% for the brain. • Body fluids and glycogen stores supply only a little over a day’s supply. • In absence of dietary carbohydrate, the needed glucose must be made from non- carbohydrate precursors. • That process is called gluconeogenesis. Slide 3 Gluconeogenesis, con’t. • Brain and muscle consume most of the glucose. • Liver and kidney are the main sites of gluconeogenesis. • Substrates include pyruvate, lactate, glycerol, most amino acids, and all TCA intermediates. • Fatty acids cannot be converted to glucose in animals. • (They can in plants because of the glyoxalate cycle.) Chapter 23, page 1 Slide 4 Remember it is necessary for the pathways to differ in some respects, Gluconeogenesis, con’t. so that the overall DG can be negative in each direction. Usually • Substrates include anything that can be converted the steps with large negative DG of to phosphoenolpyruvate . one pathway are replaced in the • Many of the reactions are the same as those in reverse pathway with reactions that glycolysis. have a large negative DG in the • All glycolytic reactions which are near equilibrium can opposite direction. operate in both directions. • The three glycolytic reactions far from equilibrium (large -DG) must be bypassed. • A side by side comparison is shown in Fig 23.1. Slide 5 Unique Reactions of Gluconeogenesis • Recall that pyruvate kinase, though named in reverse, is not reversible and has a DG of –23 kJ/mol.
  • LC-MS Resource Guide a Comprehensive Portfolio for Consistent Results in Routine and Advanced LC-MS Applications

    LC-MS Resource Guide a Comprehensive Portfolio for Consistent Results in Routine and Advanced LC-MS Applications

    LC-MS Resource Guide A Comprehensive Portfolio for Consistent Results in Routine and Advanced LC-MS applications The life science business of Merck KGaA, Darmstadt, Germany operates as MilliporeSigma in the U.S. and Canada. LC-MS Resource Guide Maximize the Performance of Your LC-MS Using Proven Consumables In this guide, we provide a premier selection of proven Supelco® tools and consumables that meet the requirements of scientists who primarily use the LC-MS technique for analysis of drugs, biomolecules separation and analytical assays. • Ascentis® Express Fused-Core® HPLC/ • Supel™-Select SPE Tubes and Well UHPLC Columns improve throughput Plates for sample prep needs and sensitivity, process more samples • SeQuant® ZIC-HILIC™ technique for and get drugs to market faster separation of polar and hydrophilic • BIOshell columns with Fused-Core® compounds technology for faster peptide, protein, • Samplicity® G2 filtration system for glycan, ADC and MAb Separations HPLC samples • Chromolith® HPLC columns with • Clean, low background LiChrosolv® revolutionary monolithic silica solvents and LiChropur® mobile phase technology for fast separation at low additives specifically designed for backpressure and long column life time UHPLC and LC-MS analysis even for Matrix-rich samples • Standards & Certified Reference • Purospher™ STAR columns with Materials for Accurate LC-MS Analyses outstanding batch-to-batch reproducibility and extended pH stability • LC-MS Accessories that maximize performance • Astec® CHIROBIOTIC® chiral stationary phases for
  • Synthesis and Antiradical Activity of Isoquercitrin Esters with Aromatic Acids and Their Homologues

    Synthesis and Antiradical Activity of Isoquercitrin Esters with Aromatic Acids and Their Homologues

    International Journal of Molecular Sciences Article Synthesis and Antiradical Activity of Isoquercitrin Esters with Aromatic Acids and Their Homologues Eva Heˇrmánková-Vavˇríková, Alena Kˇrenková, Lucie Petrásková, Christopher Steven Chambers, Jakub Zápal, Marek Kuzma, KateˇrinaValentová * and Vladimír Kˇren Laboratory of Biotransformation, Institute of Microbiology, Czech Academy of Sciences, Vídeˇnská 1083, CZ-142 20 Prague, Czech Republic; [email protected] (E.H.-V.); [email protected] (A.K.); [email protected] (L.P.); [email protected] (C.S.C.); [email protected] (J.Z.); [email protected] (M.K.); [email protected] (V.K.) * Correspondence: [email protected]; Tel.: +420-296-442-509 Academic Editor: Yujiro Hayashi Received: 27 April 2017; Accepted: 13 May 2017; Published: 17 May 2017 Abstract: Isoquercitrin, (IQ, quercetin-3-O-β-D-glucopyranoside) is known for strong chemoprotectant activities. Acylation of flavonoid glucosides with carboxylic acids containing an aromatic ring brings entirely new properties to these compounds. Here, we describe the chemical and enzymatic synthesis of a series of IQ derivatives at the C-600. IQ benzoate, phenylacetate, phenylpropanoate and cinnamate were prepared from respective vinyl esters using Novozym 435 (Lipase B from Candida antarctica immobilized on acrylic resin). The enzymatic procedure gave no products with “hydroxyaromatic” acids, their vinyl esters nor with their benzyl-protected forms. A chemical protection/deprotection method using Steglich reaction yielded IQ 4-hydroxybenzoate, vanillate and gallate. In case of p-coumaric, caffeic, and ferulic acid, the deprotection lead to the saturation of the double bonds at the phenylpropanoic moiety and yielded 4-hydroxy-, 3,4-dihydroxy- and 3-methoxy-4-hydroxy-phenylpropanoates.
  • Deliverable 1.5 Model of Plant Photosynthesis

    Deliverable 1.5 Model of Plant Photosynthesis

    PROJECT ACRONYM: FutureAgriculture PROJECT TITLE: Transforming the future of agriculture through synthetic photorespiration Deliverable 1.5 Model of plant photosynthesis TOPIC H2020-FETOPEN-2014-2015-RIA GA 686330 Arren Bar-Even CONTACT PERSON [email protected] NATURE Report (R) DISSEMINATION LEVEL PU DUE DATE 31/12/2018 ACTUAL DELIVERED DATE 14/12/2018 AUTHOR Christian Edlich-Muth This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 686330. Table of Revisions REVISION NUMBER DATE WORK PERFORMED CONTRIBUTOR(S) 1 05/12/2018 Document preparation MPIMP 2 06/12/2018 Formatting IN 3 13/12/2018 Revision Consortium D1.5 – Model of plant photosynthesis Page 2 03/04/2018 Contents 1ExecutiveSummary 5 2Cooperationbetweenparticipants 6 3 Core report 7 3.1 Theory............................................. 7 3.1.1 Pathways . 7 3.1.2 The stoichiometric consumer model of photosynthesis . 9 3.1.3 Stoichiometric-kineticmodel. 13 3.1.4 Physicochemicalparameters. 24 3.2 Results............................................. 27 3.2.1 Parametersandvariables .............................. 27 3.2.2 Rubiscokinetics ................................... 28 3.2.3 Limitation by light . 30 3.2.4 LimitationbyenzymeactivitiesotherthanRubisco. 31 3.2.5 Limitation by a Calvin cycle enzyme . 31 3.2.6 Limitationbyaphotorespiratoryenzyme . 34 3.2.7 Limitationbyaphotorespirationcarboxylase . 35 4 Conclusions 37 D1.5Modelofplantphotosynthesis Page3 03/04/2018 Table of Charts 1 Bypass coefficients ........................................ 11 2 Flux distribtion of the Calvin cycle and photorespiratory bypasses . 20 3 Kinetic constants of Rubisco and carbon dioxide diffusion .................. 28 4 Calvin cycle enzyme total activities . 33 Table of Figures 1 Energy requirements of native photorespiration and the Calvin cycle .
  • Pentose Phosphate Pathway

    Pentose Phosphate Pathway

    CH 4. HMP Pentose Phosphate Pathway Pentose Phosphate Pathway Other names: Phosphogluconate Pathway Hexose Monophosphate Shunt The linear part of the pathway carries out oxidation and decarboxylation of the 6-C sugar glucose-6-P, producing the 5-C sugar ribulose-5-P. 1 2 CH 4. HMP Glucose metabolism via the oxidative pentose phosphate pathways and relationship with glycolysis. Principal cellular functions of the pathways are indicated, and roles of NADPH included. G6PDH, glucose 6-phosphate dehydrogenase; PGDH, 6- 3 phosphogluconate dehydrogenase; RPE, ribulose-5-phosphate 3-epimerase; RPI, ribose 5-phosphate isomerase; TKL, transketolase. CH 4. HMP Hexose Monophosphate Pathway CH 4. HMP 4 Hexose Monophosphate Pathway It consists of two irreversible oxidative reactions, followed by a series of reversible sugar-phosphate interconversions No ATP is directly consumed or produced in the cycle. Carbon 1 of glucose 6-phosphate is released as CO2, and two NADPH are produced for each glucose 6-phosphate entering the oxidative part of the pathway. 5 CH 4. HMP The rate and direction of the reactions at any given time are determined by the supply of and demand for intermediates in the cycle. The HMP occurs in the cytosol of the cell. The pathway provides a major portion of the cell's NADPH, which functions as a biochemical reductant. The HMP also produces ribose-phosphate, required for biosynthesis of nucleotides, 6 CH 4. HMP for each molecule of glucose 6-phosphate oxidized. 1. Dehydrogenation of glucose 6-phosphate 2. Hydrolysis of 6- phosphogluconolactone and formation of ribulose 5- phosphate. The oxidative portion of the HMP leads to the formation of -two molecules of NADPH -CO2, and -ribulose 5-phosphate, 7 CH 4.