DOCSLIB.ORG

The Radiochemistry of Vanadium

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
The Radiochemistry of Vanadium —.—. .. — —.-—- — .— - —. .—— . v I Sciences National Research Council NUCLEAR SCIENCE SERIES The Radiochemistry of vanadium r—----\ =. _._. ._— .. COMMITTEE ON NUCLEAR SCIENCE 4. L.F.CURTISS,Chairnaun ROBLEY D.EVANS,ViceCkuirman NationalBureayofStandards MaesaohusettsInstituteofTechnology J.A.DeJUREN,Secretary WestinghouseElectricCorporation C.J.BORKOWSKI J.W. fRVINE,JR. OakRidgeNationalLaboratory MassachusettsInstituteofTechnology ROBERT G.COCHM ~~ E.D.KLEMA TexasAgriculturalandMechanical NorthwesternUniversity College W. WAYNE MEINKE sAMUEL EPSTEIN UniversityofMichigan CaliforniaInstituteofTechnology J.J.NfCKSON U.FANO MemorialHospital,New York NationalBureauofStandards ROBERT L.PLATZMAN Laboxiatoirede CbimiePhysique HERBERT GOLDSTEIN NuclearDevelopmentCorporationof D.M. VAN PATTER America BartolResesrohFoundation LIAISON MEMBERS PAUL C.AEBERSOLD CHARLES K.REED AtomicEnergyCommlsaion U.S.AirForce J.HOWARD McMILLEN WILLIAM E.WRIGHT NationalScienceFoundation Officeof NavalResearch SUBCOMMITTEE ON RADIOCHEMISTRY W. WAYNE MEINKE,Chairman HAROLD KIRBY UniversityofMichigan MoundLaboratory GREGORY R.CHOPPIN GEORGE LEDDICOTTE FloridaStateUniversity OakRidgeNationalLaboratory GEORGE A.COWAN JULIANNIELSEN LosAlamosScientificLaboratory HanfordLaboratories ARTHUR W. FALRHALL ELLISP.STEINBERG lJntversi@ofWashington ArgonneNationalLaboratory JEROME HUDIS PETER C.STEVENSON BrookbavenNationalLaboratory UniversityofCalifornia(Livermore) EARL HYDE LEO YAFFE UniversityofCalifornia(Berkeley) McGU1 University CONSULTANTS NATHAN BA LLOU JAMES DeVOE Centred’Etudedel’EnergieNucleaire UniversityofMichigan Mol-Donk,Belgium WILLIAM MARLOW, NationalBureauofStandardfl CHEMISTRY c’ + The Radiochemistry of vanadium By J. L. BROWNLEE, JR. Department of Chemistry University of Michigun Ann Arbor, Michigan December1960 subcommittee on Radicichemistry National Academy of Sciences —National Research Council Printed in USA. Price $0.75. Available from the Office of Technical Services,Departmentof Commerce, Waddngtcm 25, D. C. FOREWORD The Subcommittee on Radlochemlstry 16 one of a number of subcommittees working under the Committee on Nuclear Science within the National Academy of Sciences - National Research council . Its members represent government, industrial, and university laboratories In the areas of nuclear chemistry and analytical chemistry The Subcommittee has concerned Itself with those areas of “nuclear science which Involve the chemist, such as the collec- tion and distribution of radlochemlcal procedures, the estab- lishment of specifications for radiochemlcally pure reagents, availability of cyclotron time for service irradiations, the place of radlochemlstry In the undergraduate college program, etc. This series of monographs has grown out of the need for up-to-date compilations of radiochemlcal information and pro- cedures. The Subcommittee has endeavored to present a series which will be of maxtium use to the working scientist and which contains the latest available information. Each mono- graph collects In one volume the pertinent information required for radlochemical work with an individual element or a group of closely related elements. An expert in the radiochemistry of the partictiar element has written the monograph, followlng a standard ~ormat developed by the Subcommittee. The Atomic Energy Commlsslon has sponsored the”printing of the series. The Subcommittee Is confident these publications wI1l be useful not only to the radlochemlst but also to the research worker h other fields such as physics, biochemistry or medicine who wishes to use radiochemlcal techniques to solve a specific problem. W. Wayne Melnke, Chairman Subcommittee on Radlochemistry 111 INTRODUCTION This volume which deals with the radiochemlstry of vanadium is one of a series of monographs on radiochemistry of’the elements. There Is Included a review of the nuclear and chemical features of particular Interest to the radioc”hemist,a discussion of prob- lems of dissolution of a sample and counting techniques, and finally, a collection of radiochemlcal procedures for the element as found in the literature. Th@ seriesof monographs will cover all elements for which radlochemlcal procedures are pertinent. Plans include revision of the monograph periodically as new techniques and procedures warrant. The reader Is therefore encouraged to call to the attention of the author any published or unpublished material on the radlochetnistry of vanadium which might be included in a re- vised version of the monograph. iv CONTENTS I. General Reviews of the Inorganic and Analytical Chemistry of Vanadium. 1 II. General RevlewE of the Radlochemi6try of Vanadium. 2 III . Table of Isotopes of Vanadium. 3 Iv. Review of Those Features of Vanadium Chemistry of C.hlef Interest to Radiochemists. 4 1. Metallic Vanadium, 4 2. Soluble Salts of Vanadium, 5 3. Insoluble Salts of Vanadium - Precipitation and Co-precipitation Characteristics. 7 4. Complex Ions of Vanadium. u 5. Chelate Complexes of Vanadium, 16 6. Extraction of Thenoyltrifluoroacetone Complexes of Vanadium into Organic Solvents, 23 7. Extraction of Vanadium into Organic Solvents. 24 a. Ion-Exchange Behavior of Vanadium, 39 v. Problems Associated with Dissolving Vanadium-Containing Ssmples. 48 VI. Counting Techniques for Vanadium Isotopes. 50 VII . Collected Radiochemical Procedures for Vanadium. 54 v The Radiochemistry of Vanadium J. L. BROWNLEE, JR. Department of Chemistry University of Michigan, Ann Arbor, Michigan I. GENERAL REVIEWS OF THE INORGANIC AND ANALYTICAL CHXMISTRY OF VANADIUM 1. Friend, J. N., “A Textbook of Inorgsnlc Chemistry, “ Vol. VI, Pt. III, Charles Griffin and Co., Ltd. , London, 1929, PP. g-li6. 2. Ephralm, F., “Das Vanadln und Seine Verblndungen, “ SanmilungChemlsche und Chemlsche-Technl sche Vortr~ge, Stuttgart , 1904, pp. 81-192. 3. FeEter, G., “Die Chemlsche technologiesdes Vanadlns,” Ssmmlung Chemlsche und Chemlsche-Technlsche Vortr&e, Stuttgart, 1914, pp. 417-495. 4. Fischer, S., “Contributions to the Knowledge of the Electrolysis of Aqueous Solutions of Vanadium Salts,” Ph.D. Thesis, Columbia University, New York, 1916. 5. Hendel, J. M.~ “A New Type of Reductor and its Application to the Determination of Iron and Vanadium,” Ph.D. Thesis, Columbia University, New York, 1922. 6. Nlcolardot, P., “Le Vanadium “ Encyclopedle Sclentlflque des Aide-Memoire, Paris, 1904. 7. Menancke~ H., “Die Quantitative Untersuchungsmethoden des Molybd!lns, Vanadium, und Wolfrsms,” Prektlsches Handbuch, M. Krayn, Berlin, 1913. 8. Frank, A. J., “Chemistry of Vanadium; A Summary of Non-Project Literature through November, 1952,” Topical Report ACCO-49, American Cyanamid Company, Raw Materials Development Laboratory, Winchester, Massachusetts, 1952. 9. Sldgwlck, N. V., “The Chemical Elements and their Compounds,” Vol. I, Oxford Unlverslty Press, Oxford, 1950, pp. 804-835. 1 10. Ephralm, F., “Inorganic Chemistry, ” Gurney and Jackson, London, 1939. 11. Hlllebrand, W. F., Lundell, G. E. F., Bright, H. A., Hoffman, J. I., “Applied Inorganle Analysis,” (2nd Ed.), John Wiley and Sons, Inc., New York, 1955, pp. 452-463. 12. Chariot, G., Bezler, ‘Quantitative Inorganic Analysis,” Methuen and Company, Ltd., London, 1957, PP. 622-628. 13. McAlplne, R. K. and Soule, B. A., “Qualltatlve Chemical Analysls,” D. van Nostrand Co., New York, 1933, PP. 391-4. 14. Noyes, A. A., Bray, W. C., “A S~stem of Qualitative Analysis for the Rare Elements, The MacMillan Co., New York, 1948. 15. Mellor, J. W., “A Comprehensive Treatise on Inorganic and Theoretical Chemistry,” Vol. IX, Lon~an’s, Green and co., London, 1929, pp. 714-836. 16. Gmelln-Kraut, “Handbuch anorganische Chemle,” Band III, Abtellung 2, C. Winter, Heidelberg, 19@, pp. 55-216. 17. Moore, R. B., Llnd, S. C., Marden, J. W., Bonardi, J. P., Davis, C. W., and Conley, J. E., “Analytical Methods for” Certain Metals,” Department of the Interior, Washington, D.C., 1923, pp. 239-28o. II. GENERAL REVIEWS OF THE RADIOCHEMISTRY OF VANADIUM 1. Ra6mnussen, S. W., and Rodden, C. J., In Rodden, C. J. (Ed.) “Analytical Chemlstm of the Manhattan Pro ect,” McGraw-Hill Book Co., Inc., New York, 1950, Pp. i59- 465. 2. Stevenson, P. C. and Hicks, H. G., “Separation, Techniques Used In Radlochemlstry,” in Beckerley, J. C., “Annual Reviews of Nuclear Science,” Vol. 3, Annual Reviews, Inc., Stanford, California, 1953, pp. 221- 234. 3. Flnston, H. L. and Mlskel, “Radlochemlcal Separation Technlquea,” ——10C. cit., Vol. 5, 1955, pp. 269-296. 4. Home, R.”A., Coryell, C. D., snd Goldrlng, L. S., “Generalized Acldlty In Radlochemlcal Separations,” ——10C. cit., VO1. 6, 1956, pp. 163-178. 5. Kraus, K. A., and Nelson, F., “Radlochemlcal Separations by Ion Exchange,” ——10C. cit., Vol. 7, 1957, PP. 31-46. Note: References 2 through 5 contain general information on radlochemlcal separations, and are not specifically vanadium separation sources. 2 111. Table of Isotopes ofVanadlum* Ralf ILfe Methad of Ieotope ($ Kmrdance~ Preparation Decay Scheme (1~ 46 0.4 flea. T146(p,n)V 46 (2) 23V T146(d,2m)#6 #7 31 min. p+1.9Mev cu(p,i3)**(3) T147(d,2n)V47 Ti46(d,n)v47 ,,2.-4?’- T147 V48 16 dOYS !9+o.6gMew T148(d,2n)#8 (4) vq16d) ~ 0.906 cu(p,E)** (3) EC 2$ 1.314 2.25 4+ 2+ o+ ~i48 V@ 33adaya E.G. 0.62 CU(P,E)**(3) ~4e(d,n)v49 m48(PJY)v% 7,2-7 p 4X1014 yearn E,C., (0,25$) V51 (99.75*) -- Naturally occurrins V52 .~ V52 3,76 min. B- 2.47 “V51(n,i)V 52 23 (2+) 52 -j 1.43 Cr52(n,p)V 52 ~55(n, a)V .2+ 1.433 Vsl(d,p)v52 o+ o % h V53 2 min. p- 2.50 ~(P, B)** (3) ~ 1.00 V54 55 ❑ et. E!-3.3 ● References for much of the data oontained h this
Load more

Recommended publications
  • Preparation and Spectral Properties of Oxomolybdenum(V) Complexes. Harry Edmond Pence II Louisiana State University and Agricultural & Mechanical College
    Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1968 Preparation and Spectral Properties of Oxomolybdenum(v) Complexes. Harry Edmond Pence II Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Pence, Harry Edmond II, "Preparation and Spectral Properties of Oxomolybdenum(v) Complexes." (1968). LSU Historical Dissertations and Theses. 1411. https://digitalcommons.lsu.edu/gradschool_disstheses/1411 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. This dissertation has been microfilmed exactly as received 68-10,753 PENCE n , Harry Edmond, 1937- PREPARATION AND SPECTRAL PROPERTIES OF OXOMOLYBDENUM(V) COMPLEXES. Louisiana State University and Agricultural and Mechanical College, Ph.D., 1968 Chemistry, inorganic University Microfilms, Inc., Ann Arbor, Michigan PREPARATION AND SPECTRAL PROPERTIES OF OXOMOLYBDENUM ( V) COMPLEXES A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Harry Edmond Pence II B.S., Bethany College, Bethany, W.Va., 1958 M.S., West Virginia University, Morgantown, W.Va., 1962 February, 1968 To Ginn ACKNOWLEDGMENTS The final creation of this dissertation has been assisted by many different individuals and it is appropriate to attempt to indicate some of these contributors and offer the sincere thanks of the author,, The most important component of this assistance has been the continual encouragement offered by parents and family.
    [Show full text]
  • Amavadin- BASED VANADIUM COMPLEXES STRUCTURAL INVESTIGATIONS TON HUBREGTSE STRUCTURALINVESTIGATIONS
    amavadin- BASED VANADIUM COMPLEXES STRUCTURAL INVESTIGATIONS TON HUBREGTSE STRUCTURAL INVESTIGATIONS STRUCTURAL UITNODIGING VOOR HET BIJWONEN VAN DE OPENBARE VERDEDIGING VAN HET PROEFSCHRIFT OF EN DE STELLINGEN OP AMAVADIN-BASED VANADIUM COMPLEXES VANADIUM AMAVADIN-BASED DINSDAG 17 APRIL 2007 OM 12.30 UUR IN DE SENAATSZAAL ITNODIGING VAN DE TECHNISCHE UNIVERSITEIT DELFT U MEKELWEG 5 DELFT Voorafgaand aan de verdediging is er om 12.00 uur een toelichting voor niet-chemici. Na afloop van de plechtigheid bent u van harte welkom op de receptie in hetzelfde gebouw. Ton Hubregtse Anna Blamanlaan 8 2104 SE Heemstede 023-5283330 [email protected] T PARANIMFEN: . HUBREGTSE Huub Hubregtse [email protected] 06-46277320 Robert de Vries 2007 [email protected] belonging to the thesis ‘Structural investigations of amavadin-based vanadium complexes’ by Ton Hubregtse 1. Strongly acidic ion-exchange resins should not be used to purify molecules that rely on non-covalent bonds. E. M. Armstrong; D. Collison; N. Ertok; C. D. Garner, Talanta , 2000 , 53 , 75–87. H. Kneifel; E. Bayer, J. Am. Chem. Soc. , 1986 , 108 , 3075–3077. 2. The rule that states that the exception proves the rule is proven because there is no exception to this rule that can prove it. 3. The NMR data of Smith et al. can much better be explained when it is considered, given the three possible ligand stereoisomers and the two possible vanadium configurations, that six enantiomeric pairs of the [V( R,S-hidba) 2]-anion can be formed instead of three. P. D. Smith et al. , J. Chem. Soc., Dalton Trans. , 1997 , 4509–4516.
    [Show full text]
  • Molecular Electronic Structures of Transition Metal Complexes I
    Structure and Bonding 142 Molecular Electronic Structures of Transition Metal Complexes I Bearbeitet von Peter Day, Jens Peder Dahl, David Michael P. Mingos 1. Auflage 2012. Buch. xvi, 216 S. Hardcover ISBN 978 3 642 27369 8 Format (B x L): 15,5 x 23,5 cm Gewicht: 514 g Weitere Fachgebiete > Chemie, Biowissenschaften, Agrarwissenschaften > Analytische Chemie > Komplexchemie Zu Inhaltsverzeichnis schnell und portofrei erhältlich bei Die Online-Fachbuchhandlung beck-shop.de ist spezialisiert auf Fachbücher, insbesondere Recht, Steuern und Wirtschaft. Im Sortiment finden Sie alle Medien (Bücher, Zeitschriften, CDs, eBooks, etc.) aller Verlage. Ergänzt wird das Programm durch Services wie Neuerscheinungsdienst oder Zusammenstellungen von Büchern zu Sonderpreisen. Der Shop führt mehr als 8 Millionen Produkte. Struct Bond (2012) 142: 17–28 DOI: 10.1007/430_2011_55 # Springer-Verlag Berlin Heidelberg 2011 Published online: 6 October 2011 Electronic Structures of Oxo-Metal Ions Jay R. Winkler and Harry B. Gray Abstract The dianionic oxo ligand occupies a very special place in coordination chemistry, owing to its ability to donate p electrons to stabilize high oxidation states of metals. The ligand field theory of multiple bonding in oxo-metal ions, which was formulated in Copenhagen 50 years ago, predicts that there must be an “oxo wall” between Fe–Ru–Os and Co–Rh–Ir in the periodic table. In this tribute to Carl Ballhausen, we review this early work as well as new developments in the field. In particular, we discuss the electronic structures of beyond-the-wall (groups 9 and 10) complexes containing metals multiply bonded to O- and N-donor ligands.
    [Show full text]
  • I STUDIES on the COORDINATION CHEMISTRY of VANADIUM
    STUDIES ON THE COORDINATION CHEMISTRY OF VANADIUM, BARIUM AND COBALAMINS A dissertation submitted to Kent State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy by Riya Mukherjee May, 2011 i Dissertation written by Riya Mukherjee B.Sc., University of Calcutta, Calcutta, India, 2000 M.Sc., University of Calcutta, Calcutta, India, 2002 Ph.D., Kent State University, 2011 Approved by ___________________________________ , Chair, Doctoral Dissertation Committee Nicola E. Brasch, Ph.D. ___________________________________ , Advisor, Doctoral Dissertation Committee Nicola E. Brasch, Ph.D. ___________________________________, Member, Doctoral Dissertation Committee Scott D. Bunge, Ph.D. ___________________________________, Member, Doctoral Dissertation Committee Derek S. Damron, Ph.D. ___________________________________, Member, Doctoral Dissertation Committee Soumitra Basu, Ph.D. ___________________________________, Graduate Faculty Representative John R. D. Stalvey, Ph.D. Accepted by _______________________________, Chair, Department of Chemistry & Biochemistry Michael J. Tubergen, Ph.D. ___________________________________ , Dean, College of Arts and Sciences John R. D. Stalvey, Ph.D. ii TABLE OF CONTENTS LIST OF FIGURES……………………………………………………………………..X LIST OF TABLES…………………………………………………………………..XVII LIST OF SCHEMES……………………………………………………………….....XX DEDICATION…………………………………………………………………...…..XXII ACKNOWLEDGEMENTS………………………………………………………..XXIII ABSTRACT……………………………………………………………………….....XXV LIST OF PUBLICATIONS…………………………………………………..……..XXX
    [Show full text]
  • Spectral Studies on Vanadyl Complexes. Thomas Russell Ortolano Louisiana State University and Agricultural & Mechanical College
    Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1964 Spectral Studies on Vanadyl Complexes. Thomas Russell Ortolano Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Ortolano, Thomas Russell, "Spectral Studies on Vanadyl Complexes." (1964). LSU Historical Dissertations and Theses. 992. https://digitalcommons.lsu.edu/gradschool_disstheses/992 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. This dissertation has been 65-3391 microfilmed exactly as received ORTOLANO, Thomas Russell, 1938- SPECTRAL STUDIES ON VANADYL COMPLEXES Louisiana State University, Ph.D., 1964 Chemistry, inorganic University Microfilms, Inc., Ann Arbor, Michigan SPECTRAL STUDIES ON VANADYL COMPLEXES A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial- fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Thomas Russell Ortolano •S., Loyola University of the South, 1960 August, 1964 ACKNOWLEDGMENTS The writer wishes to express his sincere appreciation to Dr. Joel Selbin, under whose direction this work was per­ formed, for his helpful guidance throughout the course of these investigations. In addition, he would like to thank Dr. Sean P. McGlynn who served as his temporary advisor this past year while Dr. Selbin was on Sabbatical Leave in Rome. Considerable gratitude is also due his wife, June, for her two and a half years of patience and encouragement.
    [Show full text]
  • Uranium and Vanadium Binding Studies for the Selective Extraction of Uranium from Seawater
    Uranium and vanadium binding studies for the selective extraction of uranium from seawater By Bernard Frederick Parker A dissertation submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Chemistry in the Graduate Division of the University of California, Berkeley Committee in charge: Professor John Arnold, Chair Professor T. Don Tilley Professor Alexander Katz Summer 2017 1 Abstract Uranium and vanadium binding studies for the selective extraction of uranium from seawater by Bernard Frederick Parker Doctor of Philosophy in Chemistry University of California, Berkeley Professor John Arnold, Chair Chapter 1 An introduction to the uranium from seawater project. Chapter 2 A non-oxo V(V) complex with glutaroimide-dioxime (H3L), a ligand for recovering uranium from seawater, was synthesized from aqueous solution as Na[V(L)2]2H2O, and the structure determined by x-ray diffraction. It is the first non-oxo V(V) complex that has been directly synthesized in and crystallized from aqueous solution. The distorted octahedral structure contains two fully deprotonated ligands (L3-) coordinating to V5+, each in a tridentate mode. Using 17O-labelled vanadate, concurrent 17O/51V/1H/13C NMR, in conjunction with ESI-MS, unprecedentedly demonstrated the stepwise displacement of the oxo V=O bonds by glutaroimide-dioxime and verified the existence of the “bare” V5+/glutaroimide-dioxime - complex, [V(L)2] , in aqueous solution. In addition, the crystal structure of an intermediate 1:1 - V(V)/glutaroimide-dioxime complex, [VO2(HL)] , in which the oxo bonds of vanadate are only partially displaced, corroborates the observations by NMR and ESI-MS.
    [Show full text]
  • The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds
    Chem. Rev. 2004, 104, 849−902 849 The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds Debbie C. Crans,* Jason J. Smee, Ernestas Gaidamauskas, and Luqin Yang Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872 Received June 6, 2003 Contents 4.2. Ribonuclease 866 4.2.1. Structural Characterization of Model 867 1. Introduction 850 Compounds for Inhibitors of Ribonuclease 2. Aqueous V(V) Chemistry and the 851 − 4.2.2. Characterization of the 867 Phosphate Vanadate Analogy Nucleoside-Vanadate Complexes that 2.1. Aqueous V(V) Chemistry 851 Form in Solution and Inhibit Ribonuclease 2.2. Mimicking Cellular Metabolites: 852 4.2.3. Vanadium−Nucleoside Complexes: 868 Vanadate−Phosphate Analogy Functional Inhibitors of Ribonuclease (Four-Coordinate Vanadium) 4.3. Other Phosphorylases 868 2.3. Structural Model Studies of Vanadate Esters 852 4.4. ATPases 869 2.4. Vanadate Esters: Functional Analogues of 853 4.4.1. Structural Precedence for the 869 Phosphate Esters Vanadate−Phosphate Anhydride Unit: 2.5. Vanadate Anhydrides: Structural Analogy 854 Five- or Six-Coordinate Vanadium with Condensed Phosphates 4.4.2. Vanadate as a Photocleavage Agent for 870 2.6. Potential Future Applications of 855 ATPases Vanadium-Containing Ground State Analogues in Enzymology 5. Amavadine and Siderophores 871 3. Haloperoxidases: V(V) Containing Enzymes and 855 5.1. Amavadine 871 Modeling Studies 5.1.1. Amavadine: Structure 871 3.1. Bromoperoxidase 855 5.1.2. Amavadine: Activities and Roles 872 3.2. Chloroperoxidase 856 5.2. Siderophores 873 3.3. From Haloperoxidases to Phosphatases 857 5.2.1.
    [Show full text]
  • Ligand Interactions in Solution
    A cw-ENDOR investigation of metal- ligand interactions in solution Submitted in canditure for the degree of Doctor of Philosophy By Richard James Tucker, M.Chem Department of Chemistry University of Wales, Cardiff September 2005 UMI Number: U585544 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Dissertation Publishing UMI U585544 Published by ProQuest LLC 2013. Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 Declaration This work has not previously been accepted in substance for any degree and is not being concurrently submitted in candidature for any degree. Signed ^ ...... (candidate) Date n - 1 - oC This thesis is the result of my own investigations, except where otherwise stated. Other sources are acknowledged by footnotes giving explicit references. A bibliography is appended. Signed (candidate) Date 0 ( 0 I hereby give consent for my thesis, if accepted, to be available for photocopying and for inter-library loan, and for the title and summary to be made available to outside organisations. Signed .... (7/.. .. .^V^T?^r777T (candidate) D ate 9 .^ . Summary Electron Nuclear DOuble Resonance (ENDOR) spectroscopy has been employed in this Thesis to study a range of paramagnetic metal-ligand complex systems.
    [Show full text]
  • Vanadyl As a Stable Structural Mimic of Reactive Ferryl Intermediates in Mononuclear Nonheme-Iron Enzymes † † § † ‡ Ryan J
    Article Cite This: Inorg. Chem. 2017, 56, 13382-13389 pubs.acs.org/IC Vanadyl as a Stable Structural Mimic of Reactive Ferryl Intermediates in Mononuclear Nonheme-Iron Enzymes † † § † ‡ Ryan J. Martinie, Christopher J. Pollock, Megan L. Matthews, J. Martin Bollinger, Jr.,*, , † ‡ † Carsten Krebs,*, , and Alexey Silakov*, † ‡ Department of Chemistry and Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, United States § Department of Chemical Physiology and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States *S Supporting Information ABSTRACT: The iron(II)- and 2-(oxo)glutarate-dependent (Fe/ 2OG) oxygenases catalyze an array of challenging transformations via a common iron(IV)-oxo (ferryl) intermediate, which in most cases abstracts hydrogen (H•) from an aliphatic carbon of the substrate. Although it has been shown that the relative disposition of the Fe−O and C−H bonds can control the rate of H• abstraction and fate of the resultant substrate radical, there remains a paucity of structural information on the actual ferryl states, owing to their high reactivity. We demonstrate here that the stable vanadyl ion [(VIV-oxo)2+] binds along with 2OG or its decarboxylation product, succinate, in the active site of two different Fe/2OG enzymes to faithfully mimic their transient ferryl states. Both ferryl and vanadyl complexes of the Fe/2OG halogenase, SyrB2, remain stably bound to its carrier protein substrate (L-aminoacyl-S-SyrB1), whereas the corresponding complexes harboring transition metals (Fe, Mn) in lower oxidation states dissociate. In the well-studied taurine:2OG dioxygenase (TauD), the disposition of the substrate C−H bond relative to the vanadyl ion defined by pulse electron paramagnetic resonance methods is consistent with the crystal structure of the reactant complex and computational models of the ferryl state.
    [Show full text]
  • Paramagnetic Resonance Studies of Invivo Vanadyl
    One and Two Dimensional Pulsed Electron Paramagnetic Resonance Studies of in vivo Vanadyl Coordination in Rat Kidney Sergei A. Dikanov,''*Barry D. Liboiron,3'+ Katherine H. Thompson, Erika Vera,4 Violet G. Yuen,4 John H. McNeill 4 and Chris Orvig'' 1Illinois EPR Research Center and Department of Veterinary Clinical Medicine, 190 MSB, 506 S. Mathews Ave., University ofIllinois at Urbana-Champaign, Urbana, IL 61801, U. S. A. Institute ofChemical Kinetics and Combustion, Russian Academy ofSciences, Novosibirsk 6300090, Russia. 3Medicinal Inorganic Chemistry Group, Department ofChemistry, University ofBritish Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada. 4Faculty ofPharmaceutical Sciences, University ofBritish Columbia, 2146 East Mall, Vancouver, BC V6T 1Z3, Canada. +Present address: Department ofChemistry, Stanford University, Stanford, CA 94305, U. S. A. (Received: November 1, 2002; Accepted: January 2, 2003) ABSTRACT The biological fate of a chelated vanadium source is investigated by/n vivo spectroscopic methods to elucidate the chemical form in which the metal ion is accumulated. A pulsed electron paramagnetic resonance study of vanadyl ions in kidney tissue, taken from rats previously treated with bis(ethylmaltolato)oxovanadium(IV) (BEOV) in drinking water, is presented. A combined approach using stimulated echo (3-pulse) electron spin echo envelope modulation (ESEEM) and the two dimensional 4-pulse hyperfine sublevel correlation (HYSCORE) spectroscopies has shown that at least some of the VO2+ ions are involved in the coordination with nitrogen-containing ligands. From the experimental spectra, a 4N hyperfine coupling constant of 4.9 MHz and a quadrupole coupling constant of 0.6 + 0.04 MHz were determined, consistent with amine coordination of the vanadyl ions.
    [Show full text]
  • Vanadium and Molybdenum Complexes with Amino Acid Functionalized Ligands
    Vanadium and Molybdenum Complexes with Amino Acid Functionalized Ligands DISSERTATION zur Erlangung des akademischen Grades doctor rerum naturalium (Dr. rer. nat.) vorgelegt dem Rat der Chemisch-Geowissenschaftlichen Fakult¨at der Friedrich-Schiller Universit¨at Jena von Food Chemist Manjola Mancka geboren am 17.04.1978 in Devoll, Albania Gutachter 1. Prof. Dr. Winfried Plass 2. Prof. Dr. Matthias Westernhausen Tag deroffentlichen ¨ Verteidigung: October 18th 2006 For my beloved parents and my Family Acknowledgements • I would like to express my heartfelt gratitude to my supervisor Prof. Dr. Winfried Plass for giving me the opportunity to work in this interesting field, I thank him for support, advises and guidance. • I also thank to Dr. Axel Buchholz, for many valuable suggestions, for much help in the single crystal analysis, and for his help in the arrangement of the thesis. • I am grateful to our research group with whom I had the pleasure of working, for their friendship, helpful discussions, and the good co-operative atmosphere. I also thank to my colleague Arne Roth for helping me in solving LATEXproblems. I would like to thank Ines Seidel for many valuable discussions about the kinetic experiments. • I moreover thank all Technical assistants of the Institut f¨ur Anorganische und Ana- lytische Chemie (IAAC) and NMR department for analyses of the samples: Dr. Popitz, Frau Sch¨onau und Frau Heineck (MS), Frau Rambach und Dr. Friedrich (NMR, EPR), Frau Lentvogt und Frau Sch¨onfeld (CHN). • Many thanks to Lotte Neupert for the HPLC measurements. • I am especially pleased to acknowledge Dr. Helmar G¨orls for measuring my X-ray crystal structures.
    [Show full text]
  • An Electron Paramagnetic Resonance Study of Vanadyl-Labeled Conalbumin and Iron Transferrins
    University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Fall 1979 AN ELECTRON PARAMAGNETIC RESONANCE STUDY OF VANADYL-LABELED CONALBUMIN AND IRON TRANSFERRINS JAMES DAVID CASEY JR. Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation CASEY, JAMES DAVID JR., "AN ELECTRON PARAMAGNETIC RESONANCE STUDY OF VANADYL-LABELED CONALBUMIN AND IRON TRANSFERRINS" (1979). Doctoral Dissertations. 1231. https://scholars.unh.edu/dissertation/1231 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. 8009661 C a s e y, Ja m e s D a v id, Jr . AN ELECTRON PARAMAGNETIC RESONANCE STUDY OF VANADYL- LABELED CONALBUMIN AND IRON TRANSFERRINS University o f New Hampshire PH.D. 1979 University Microfilms International300 N. Zeeb Road, Ann Arbor, MI 48106 18 Bedford Row, London WC1R 4EJ, England AN ELECTRON PARAMAGNETIC RESONANCE STUDY OF VANADYL-LABELED CONALBUMIN AND IRON TRANSFERRINS BY JAMES DAVID CASEY JR. B.S., Boston College, 1968 A DISSERTATION Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemistry September, 1979 This thesis has been examined and approved. Thesis director, N. Dennis Chasteen Professor of Chemistry Vu. ■ V c k , Helmut M. Haendler, Professor of Chemistry ^TTVl^Ywa . Morrison, Professor of Chemistry Q (7James A. Stewart, Associate Professor of Biochemistry Rudolf W.
    [Show full text]