Selenium Vs. Sulfur: Investigating the Substrate Specificity of a Selenocysteine Lyase
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Identification and Characterization of a Selenoprotein Family Containing a Diselenide Bond in a Redox Motif
Identification and characterization of a selenoprotein family containing a diselenide bond in a redox motif Valentina A. Shchedrina, Sergey V. Novoselov, Mikalai Yu. Malinouski, and Vadim N. Gladyshev* Department of Biochemistry, University of Nebraska, Lincoln, NE 68588-0664 Edited by Arne Holmgren, Karolinska Institute, Stockholm, Sweden, and accepted by the Editorial Board July 13, 2007 (received for review April 16, 2007) Selenocysteine (Sec, U) insertion into proteins is directed by trans- notable exception. Vertebrate selenoprotein P (SelP) has 10–18 lational recoding of specific UGA codons located upstream of a Sec, whose insertion is governed by two SECIS elements (11). It is stem-loop structure known as Sec insertion sequence (SECIS) ele- thought that Sec residues in SelP (perhaps with the exception of the ment. Selenoproteins with known functions are oxidoreductases N-terminal Sec residue present in a UxxC motif) have no redox or containing a single redox-active Sec in their active sites. In this other catalytic functions. work, we identified a family of selenoproteins, designated SelL, Selenoproteins with known functions are oxidoreductases con- containing two Sec separated by two other residues to form a taining catalytic redox-active Sec (12). Their Cys mutants are UxxU motif. SelL proteins show an unusual occurrence, being typically 100–1,000 times less active (13). Although there are many present in diverse aquatic organisms, including fish, invertebrates, known selenoproteins, proteins containing diselenide bonds have and marine bacteria. Both eukaryotic and bacterial SelL genes use not been described. Theoretically, such proteins could exist, but the single SECIS elements for insertion of two Sec. -
The Selenium Recycling Enzyme Selenocysteine Lyase: Regulation and Physiological Role in Glucose and Lipid Metabolism
THE SELENIUM RECYCLING ENZYME SELENOCYSTEINE LYASE: REGULATION AND PHYSIOLOGICAL ROLE IN GLUCOSE AND LIPID METABOLISM A DISSERTATION SUBMITTED TO THE GRADUATE DIVISION OF THE UNIVERSITY OF HAWAI‘I AT MĀNOA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN CELL AND MOLECULAR BIOLOGY MAY 2012 BY LUCIA ANDREIA SEALE Dissertation Committee: Marla J. Berry, Chairperson Robert A. Nichols Jun Pane‘e P. Reed Larsen E. Gordon Grau To my beloved parents Wilson & Madalena To my dear love André ii ACKNOWLEDGEMENTS A Ph.D. is a journey in a rough sea. As in all memorable expeditions, there is more to learn while traveling towards the final destination than at the destination itself. In several ways, it is the path and how you face the unexpected obstacles in this path that makes you a Doctor. The Ph.D. expedition does not allow an easy ride. While you travel through the waves and storms of your topic, figuring out a lot on and about yourself, you also encounter along the way people that make your stressful journey happier, nicer, safer, funnier and – why not – more challenging. They provided the emotional background that is not described in a scientific document. In my Ph.D. journey, these are the people about whom I’ll talk years ahead to friends, to whom I will silently smile when the nostalgic waves of the Ph.D. path break in the shores of my life. They are the unforgettable people that allowed me to arrive safe and sound in Doctorland. First and foremost, my greatest acknowledgement and gratitude goes to Dr. -
The Deiodination of Thyroid Hormone in Rat Liver
The deiodination of thyroid hormone in rat liver De dejodering van schildklierhormoon in de lever van de rat PROEFSCHRIFT T er verkrijging van de graad van doctor in de geneeskunde aan de Erasmus Universiteit Rotterdam op gezag van de rector magnificus prof. dr. M. W. van Hof en vo1gens bes1uit van het college van dekanen. De openbare verdediging zal p1aatsvinden op woensdag 12 juni 1985 te 15.45 uur door Jan Adrianus Mol geboren te Dordrecht BEGELEIDINGSCOMMISSIE PROMOTOR PROF. DR. G. HENNEMANN OVERIGE LEDEN PROF. DR. W.C. HuLSMANN PROF. DR. H.J. VANDER MOLEN PROF. DR. H.J. VAN EIJK The studies in this thesis were carried out under the direction of Dr. T.J. Visser in the laboratory of the Thyroid Hormone Research Unit (head Prof. Dr. G. Hennemann) at the Department of Internal Medicine III and Clinical ·Endocrinology (head Prof. Dr. J.c. Birkenhager), Erasmus University Medical School, Rotterdam, The Netherlands. The investigations were supported by grant 13-34-108 from the Foundation for Medical Research FUNGO. Kennis, zij zal afgedaan hebben •... zo blijven dan: Geloof, hoop en liefde •.•. (I Korintiers 13) aan mijn Ouders aan Ellen, Gerben en Jurjan CONTENTS List of abbreviations. 7 Chapter I General introduction. 9 Chapter II The liver, a central organ for iodothyronine 17 metabolism? Chapter III Synthesis and some properties of sulfate 45 esters and sulfamates o_f iodothyronines. Chapter IV Rapid and selective inner ring deiodination 61 of T4 sulfate by rat liver deiodinase. Chapter V Modification of rat liver iodothyronine 75 5'-deiodinase activity with diethylpyrocarbo nate and Rose Bengal: evidence for an active site histidine residue. -
Selenocysteine, Pyrrolysine, and the Unique Energy Metabolism of Methanogenic Archaea
Hindawi Publishing Corporation Archaea Volume 2010, Article ID 453642, 14 pages doi:10.1155/2010/453642 Review Article Selenocysteine, Pyrrolysine, and the Unique Energy Metabolism of Methanogenic Archaea Michael Rother1 and Joseph A. Krzycki2 1 Institut fur¨ Molekulare Biowissenschaften, Molekulare Mikrobiologie & Bioenergetik, Johann Wolfgang Goethe-Universitat,¨ Max-von-Laue-Str. 9, 60438 Frankfurt am Main, Germany 2 Department of Microbiology, The Ohio State University, 376 Biological Sciences Building 484 West 12th Avenue Columbus, OH 43210-1292, USA Correspondence should be addressed to Michael Rother, [email protected] andJosephA.Krzycki,[email protected] Received 15 June 2010; Accepted 13 July 2010 Academic Editor: Jerry Eichler Copyright © 2010 M. Rother and J. A. Krzycki. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Methanogenic archaea are a group of strictly anaerobic microorganisms characterized by their strict dependence on the process of methanogenesis for energy conservation. Among the archaea, they are also the only known group synthesizing proteins containing selenocysteine or pyrrolysine. All but one of the known archaeal pyrrolysine-containing and all but two of the confirmed archaeal selenocysteine-containing protein are involved in methanogenesis. Synthesis of these proteins proceeds through suppression of translational stop codons but otherwise the two systems are fundamentally different. This paper highlights these differences and summarizes the recent developments in selenocysteine- and pyrrolysine-related research on archaea and aims to put this knowledge into the context of their unique energy metabolism. 1. Introduction found to correspond to pyrrolysine in the crystal structure [9, 10] and have its own tRNA [11]. -
Growthmechanismand Characteristics of Semiconductor Nanowires For
www.symbiosisonline.org Symbiosis www.symbiosisonlinepublishing.com Research Article Nanoscience & Technology: Open Access Open Access Growth Mechanism and Characteristics of Semiconductor Nanowires for Photonic Devices N. B Singh1, S. R Coriell1, Matthew King2, Brian Wagner2, David Kahler2, David Knuteson2, Andre Berghman2 and Sean McLaughlin2 1University of Maryland Baltimore County, 1000 Hilltop Circle, Baltimore, MD 21250 2Northrop Grumman Corporation ES, 1212 Winterson Road, Linthicum, MD 21250 Received: March 31, 2014; Accepted: April 27, 2014; Published: April 29, 2014 *Corresponding author: N. B Singh, University of Maryland Baltimore County, 1000 Hilltop Circle, Baltimore, MD 21250 photodiodes (A Abstract photon counting applications. These arecapable of low-light An overview on the growth mechanism of nanowire, fabrication detectionand havePDs) great are potentialvery capable for the detectors variety ofin applications. finding and and performance of selenide nanowires devices is presented. Growth of nano particles and preliminary results on the formation Binary, ternary and quaternary selenides have relatively low optical of nanowires of lead selenide is reported. Results are presented for the zinc selenide nanowire based devices, performance and combination of properties of selenides makes them very important materialsabsorption for coefficient detector andapplications. have wide Lead transparency selenide (PbSe)range. nanoThis particles and nanowires were grown by the physical vapor transport to device arrays. (PVT) method and zinc selenide (ZnSe) nanowire was grown by more specifically the ability to transition from single NW devices chemical vapor transport (CVT) methods. Observations on the growth Experimental Method of PbSe indicate that oriented attachment of nanocrystal building Materials purification blocks produces nanowires. On silicon (111) substrates binding was observed to be on (001) and (111) faces. -
Selenocysteine, Identified As the Penultimate C-Terminal Residue in Human T-Cell Thioredoxin Reductase, Corresponds to TGA in the Human Placental Gene" (1996)
University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln Vadim Gladyshev Publications Biochemistry, Department of June 1996 Selenocysteine, identified as the penultimate C-terminal esiduer in human T-cell thioredoxin reductase, corresponds to TGA in the human placental gene Vadim Gladyshev University of Nebraska-Lincoln, [email protected] Kuan-Teh Jeang National Institutes of Health, Bethesda, MD Thressa C. Stadtman National Institutes of Health, Bethesda, MD Follow this and additional works at: https://digitalcommons.unl.edu/biochemgladyshev Part of the Biochemistry, Biophysics, and Structural Biology Commons Gladyshev, Vadim; Jeang, Kuan-Teh; and Stadtman, Thressa C., "Selenocysteine, identified as the penultimate C-terminal residue in human T-cell thioredoxin reductase, corresponds to TGA in the human placental gene" (1996). Vadim Gladyshev Publications. 23. https://digitalcommons.unl.edu/biochemgladyshev/23 This Article is brought to you for free and open access by the Biochemistry, Department of at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in Vadim Gladyshev Publications by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. Proc. Natl. Acad. Sci. USA Vol. 93, 6146-6151, June 1996 Biochemistrypp. Selenocysteine, identified as the penultimate C-terminal residue in human T-cell thioredoxin reductase, corresponds to TGA in the human placental gene (selenium/thioredoxin reductase/TGA/selenocysteine) VADIM N. GLADYSHEV*, KUAN-TEH JEANGt, AND THRESSA C. STADTMAN*t *Laboratory of Biochemistry, National Heart, Lung, and Blood Institute, and tLaboratory of Molecular Microbiology, National Institute of Allergy and Infectious Diseases, National Institutes of Health, 9000 Rockville Pike, Bethesda, MD 20892 Contributed by Thressa C. Stadtman, February 27, 1996 ABSTRACT The possible relationship of selenium to im- peroxidase family (8). -
Characterization of a Selenocysteine-Ligated P450 Compound I Reveals Direct Link Between Electron Donation and Reactivity Elizab
Characterization of a Selenocysteine-ligated P450 Compound I Reveals Direct Link Between Electron Donation and Reactivity Elizabeth Onderko†, Alexey Silakov†, Timothy H. Yosca‡, and Michael T. Green‡,* ‡Departments of Chemistry & Molecular Biology and Biochemistry, University of California, Irvine, CA 92697 †Department of Chemistry, Penn State University, University Park, PA 16802 Contact: [email protected] Abstract Strong electron-donation from the axial thiolate-ligand of cytochrome P450 has been proposed to increase the reactivity of compound I with respect to C–H bond activation. However, it has proven difficult to test this hypothesis, and a direct link between reactivity and electron donation has yet to be established. To make this connection, we have prepared a selenolate-ligated cytochrome P450 compound I intermediate. This isoelectronic perturbation allows for direct comparisons with the wild type enzyme. Selenium incorporation was obtained using a cysteine auxotrophic E. coli strain. The intermediate was prepared with meta-chloroperbenzoic acid and characterized by UV-visible, Mössbauer, and electron paramagnetic resonance spectroscopies. Measurements revealed increased asymmetry around the ferryl moiety, consistent with increased electron donation from the axial selenolate-ligand. In line with this observation, we find that the selenolate-ligated compound I cleaves C–H bonds more rapidly than the wild-type intermediate. Background Cytochrome P450s are a class of thiolate-ligated heme proteins that are known for their ability to functionalize unactivated C–H bonds. In efforts to understand reactivity in these and other thiolate-heme systems, comparisons are often drawn between P450s and the histidine-ligated heme peroxidases. Both classes of heme enzymes share a similar active intermediate: a ferryl (or iron(IV)oxo) radical species, called compound I1-3. -
Generation of Recombinant Mammalian Selenoproteins Through Ge- Netic Code Expansion with Photocaged Selenocysteine
bioRxiv preprint doi: https://doi.org/10.1101/759662; this version posted September 5, 2019. The copyright holder for this preprint (which was not certified by peer review) is the author/funder. All rights reserved. No reuse allowed without permission. Generation of Recombinant Mammalian Selenoproteins through Ge- netic Code Expansion with Photocaged Selenocysteine. Jennifer C. Peeler, Rachel E. Kelemen, Masahiro Abo, Laura C. Edinger, Jingjia Chen, Abhishek Chat- terjee*, Eranthie Weerapana* Department of Chemistry, Boston College, Chestnut Hill, Massachusetts 02467, United States Supporting Information Placeholder ABSTRACT: Selenoproteins contain the amino acid sele- neurons susceptible to ferroptotic cell death due to nocysteine and are found in all domains of life. The func- overoxidation and inactivation of GPX4-Cys.4 This ob- tions of many selenoproteins are poorly understood, servation demonstrates a potential advantage conferred partly due to difficulties in producing recombinant sele- by the energetically expensive production of selenopro- noproteins for cell-biological evaluation. Endogenous teins. mammalian selenoproteins are produced through a non- Sec incorporation deviates from canonical protein canonical translation mechanism requiring suppression of translation, requiring suppression of the UGA stop codon. the UGA stop codon, and a selenocysteine insertion se- In eukaryotes, Sec biosynthesis occurs directly on the quence (SECIS) element in the 3’ untranslated region of suppressor tRNA (tRNA[Ser]Sec). Specifically, tRNA[Ser]Sec the mRNA. Here, recombinant selenoproteins are gener- is aminoacylated with serine by seryl-tRNA synthetase ated in mammalian cells through genetic code expansion, (SerS), followed by phosphorylation by phosphoseryl- circumventing the requirement for the SECIS element, tRNA kinase (PSTK), and subsequent Se incorporation and selenium availability. -
Site-Specific Protein Modifications Through Pyrroline-Carboxy-Lysine Residues
Site-specific protein modifications through pyrroline-carboxy-lysine residues Weijia Ou1, Tetsuo Uno1, Hsien-Po Chiu, Jan Grünewald, Susan E. Cellitti, Tiffany Crossgrove, Xueshi Hao, Qian Fan, Lisa L. Quinn, Paula Patterson, Linda Okach, David H. Jones, Scott A. Lesley, Ansgar Brock, and Bernhard H. Geierstanger2 Genomics Institute of the Novartis Research Foundation, 10675 John-Jay-Hopkins Drive, San Diego, CA 92121-1125 Edited* by Peter G. Schultz, The Scripps Research Institute, La Jolla, CA, and approved May 11, 2011 (received for review April 4, 2011) Pyrroline-carboxy-lysine (Pcl) is a demethylated form of pyrrolysine acids will face similar hurdles to achieve site-specificity without that is generated by the pyrrolysine biosynthetic enzymes when deleterious effects to the protein of interest. the growth media is supplemented with D-ornithine. Pcl is readily The most elegant way to generate homogenously, site-specifi- incorporated by the unmodified pyrrolysyl-tRNA/tRNA synthetase cally modified proteins is the in vivo incorporation of unnatural pair into proteins expressed in Escherichia coli and in mammalian amino acids (7–9). Over 70 unnatural amino acids featuring a cells. Here, we describe a broadly applicable conjugation chemistry wide array of functionalities can be incorporated at TAG codons that is specific for Pcl and orthogonal to all other reactive groups using specific tRNA/tRNA synthetase pairs engineered through on proteins. The reaction of Pcl with 2-amino-benzaldehyde or an in vivo selection process to be orthogonal to the cellular 2-amino-acetophenone reagents proceeds to near completion at machinery of the host cells. A set of reactive unnatural amino neutral pH with high efficiency. -
Trends in Performance Limits of the HOT Infrared Photodetectors
applied sciences Review Trends in Performance Limits of the HOT Infrared Photodetectors Antoni Rogalski 1, Piotr Martyniuk 1,*, Małgorzata Kopytko 1 and Weida Hu 2 1 Faculty of Advanced Technologies and Chemistry, Institute of Applied Physics, Military University of Technology, 2 Kaliskiego St., 00-908 Warsaw, Poland; [email protected] (A.R.); [email protected] (M.K.) 2 State Key Laboratory of Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, 500 Yu Tian Road, Shanghai 200083, China; [email protected] * Correspondence: [email protected]; Tel.: +48-26-183-92-15 Abstract: The cryogenic cooling of infrared (IR) photon detectors optimized for the mid- (MWIR, 3–5 µm) and long wavelength (LWIR, 8–14 µm) range is required to reach high performance. This is a major obstacle for more extensive use of IR technology. Focal plane arrays (FPAs) based on thermal detectors are presently used in staring thermal imagers operating at room temperature. However, their performance is modest; thermal detectors exhibit slow response, and the multispectral detection is difficult to reach. Initial efforts to develop high operating temperature (HOT) photodetectors were focused on HgCdTe photoconductors and photoelectromagnetic detectors. The technological efforts have been lately directed on advanced heterojunction photovoltaic HgCdTe detectors. This paper presents the several approaches to increase the photon-detectors room-temperature performance. Various kinds of materials are considered: HgCdTe, type-II AIIIBV superlattices, two-dimensional materials and colloidal quantum dots. Keywords: HOT IR detectors; HgCdTe; P-i-N; BLIP condition; 2D material photodetectors; colloidal quantum dot photodetectors Citation: Rogalski, A.; Martyniuk, P.; Kopytko, M.; Hu, W. -
Biochemical Mechanisms of Thyroid Hormone Deiodination
THYROID Volume 15, Number 8, 2005 © Mary Ann Liebert, Inc. Biochemical Mechanisms of Thyroid Hormone Deiodination George G.J.M. Kuiper, Monique H.A. Kester, Robin P. Peeters, and Theo J. Visser Deiodination is the foremost pathway of thyroid hormone metabolism not only in quantitative terms but also because thyroxine (T4) is activated by outer ring deiodination (ORD) to 3,3’,5-triiodothyronine (T3), whereas both T4 and T3 are inactivated by inner ring deiodination (IRD) to 3,3’,5-triiodothyronine and 3,3’- diiodothyronine, respectively. These reactions are catalyzed by three iodothyronine deiodinases, D1-3. Although they are homologous selenoproteins, they differ in important respects such as catalysis of ORD and/or IRD, deiodination of sulfated iodothyronines, inhibition by the thyrostatic drug propylthiouracil, and regulation during fetal and neonatal development, by thyroid state, and during illness. In this review we will briefly discuss recent developments in these different areas. These have resulted in the emerging view that the biological activity of thyroid hormone is regulated locally by tissue-specific regulation of the different deiodinases. HYROID HORMONE is essential for growth, development, thyrostatic drug 6-propyl-2-thiouracil (PTU). D1 activity is Tand regulation of energy metabolism (1–3). Amphibian positively regulated by T3, reflecting regulation of D1 ex- metamorphosis is an important example of thyroid hormone pression by T3 at the pretranslational level. actions on development (4). Equally well known is the crit- In humans, D2 activity is found in brain, anterior pitu- ical role of thyroid hormone in development and function itary, placenta, thyroid and skeletal muscle, and D2 mRNA of the human central nervous system (5,6). -
Thyroid-Modulating Activities of Olive and Its Polyphenols: a Systematic Review
nutrients Review Thyroid-Modulating Activities of Olive and Its Polyphenols: A Systematic Review Kok-Lun Pang 1,† , Johanna Nathania Lumintang 2,† and Kok-Yong Chin 1,* 1 Department of Pharmacology, Faculty of Medicine, Universiti Kebangsaan Malaysia, Jalan Yaacob Latif, Bandar Tun Razak, Cheras 56000, Kuala Lumpur, Malaysia; [email protected] 2 Faculty of Applied Sciences, UCSI University Kuala Lumpur Campus, Jalan Menara Gading, Taman Connaught, Cheras 56000, Kuala Lumpur, Malaysia; [email protected] * Correspondence: [email protected]; Tel.: +60-3-91459573 † These authors contributed equally to this work. Abstract: Olive oil, which is commonly used in the Mediterranean diet, is known for its health benefits related to the reduction of the risks of cancer, coronary heart disease, hypertension, and neurodegenerative disease. These unique properties are attributed to the phytochemicals with potent antioxidant activities in olive oil. Olive leaf also harbours similar bioactive compounds. Several studies have reported the effects of olive phenolics, olive oil, and leaf extract in the modulation of thyroid activities. A systematic review of the literature was conducted to identify relevant studies on the effects of olive derivatives on thyroid function. A comprehensive search was conducted in October 2020 using the PubMed, Scopus, and Web of Science databases. Cellular, animal, and human studies reporting the effects of olive derivatives, including olive phenolics, olive oil, and leaf extracts on thyroid function were considered. The literature search found 445 articles on this topic, but only nine articles were included based on the inclusion and exclusion criteria. All included articles were animal studies involving the administration of olive oil, olive leaf extract, or olive pomace residues orally.