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Bioinorganic Chemistry Module No and Title 1: Introduction Subject Chemistry Paper No and Title 15: Bioinorganic Chemistry Module No and 1: Introduction: Bioinorganic Chemistry Title Module Tag CHE_P15_M1 CHEMISTRY Paper No. 15: Bioinorganic Chemistry Module No. 1: Introduction: Bioinorganic Chemistry TABLE OF CONTENTS 1. Learning Outcomes 2. Introduction 3. Metal function in Metalloproteins 4. Functions of metalloenzymes 5. Communication roles for metals in Biology 6. Interactions of metal ions and nucleic acids 7. Metal-Ion Transport and Storage 7.1 General aspects of storage and transport of metal-ions 7.2 Iron: Function, Storage and Transport 7.2.1. Function 7.2.2. Iron storage 7.2.2.1. Ferritin 7.2.2.2. Hemosiderin 7.2.3. Transport of Iron: Transferrin 7.3 Calcium: Function, Storage and Transport 7.3.1. Function 7.3.2. Calcium Storage 7.3.3. Calcium Pump 7.4 Copper: Function, Storage and Transport 7.4.1. Function 7.4.2. Storage of Copper 7.4.3. Copper transport 8. Summary CHEMISTRY Paper No. 15: Bioinorganic Chemistry Module No. 1: Introduction: Bioinorganic Chemistry 1. Learning Outcomes After studying this module, you shall be able to Know the importance of inorganic elements. Categorize the inorganic elements according to their roles in the biological system. Learn the function of important elements such as Iron, Calcium and Copper. Identify the general aspects of storage and transport of metal-ions. Know the role of metals in medicine. 2. Introduction Bioinorganic chemistry constitutes the discipline at the interface of the more classical areas of inorganic chemistry and biology. Although biology is generally related to organic chemistry, inorganic elements are also important to life processes. Table 1 lists the essential inorganic elements together with some of their known roles in biology. Bioinorganic chemists study these inorganic species according to their function in vivo. Inorganic elements have also been artificially introduced into biological systems as probes of structure and function. Heavy metals such as mercury and platinum are used by X-ray crystallographers and electron microscopists to help elucidate the structures of macromolecules. Paramagnetic metal ions have been valuable in magnetic-resonance applications. Metal-containing compounds have been used not only as biological probes, but also as diagnostic and therapeutic pharmaceuticals. The mechanisms of action of platinum anticancer drugs, gold antiarthritic agents, and technetium radiopharmaceuticals are some currently active topics of investigation in bioinorganic chemistry. Bioinorganic chemistry, thus has two major components: the study of naturally occurring inorganic elements in biology and the introduction of metals into biological systems as probes and drugs. Peripheral but essential aspects of the discipline include investigations of inorganic elements in nutrition, of the toxicity of inorganic species (including the ways in which such toxicities are overcome both by the natural systems and by human intervention), and storage and transport of metal-ions in biology. Table 1. Essential inorganic elements and their role in biology. Metal Function Sodium Charge carrier; osmotic balance Potassium Charge carrier; osmotic balance Magnesium Structure; hydrolase; isomerase Calcium Structure: trigger; charge carrier Vanadium Nitrogen fixation; oxidase Molybdenum Nitrogen fixation; oxidase; oxo transfer Tungsten Dehydrogenase CHEMISTRY Paper No. 15: Bioinorganic Chemistry Module No. 1: Introduction: Bioinorganic Chemistry Manganese Photosynthesis; oxidase; structure Iron Oxidase; dioxygen tramped and storage; electron transfer: nitrogen fixation Cobalt Oxidase; alkyl group transfer Nickel Hydrogenase; hydrolase Copper Oxidase; dioxygen transport: electron transfer Zinc Structure; hydrolase 3. Metal Function in Metalloproteins Metals are commonly found as natural constituents of proteins. Nature has learned to use the special properties of metal ions to perform a wide variety of specific functions associated with life processes. Metalloproteins that perform a catalytic function are called metalloenzymes. Metalloproteins are a class of biologically important macromolecules and account for nearly half of all proteins in biology. They are responsible for performing some of the most difficult yet important functions, including photosynthesis, respiration, water oxidation, oxygen transport, electron transfer, oxygenation and nitrogen fixation. 4. Functions of Metalloenzyme Metalloenzymes are a subclass of metalloproteins that perform specific catalytic functions. A net chemical transformation occurs in the molecule, termed a substrate, being acted upon by the metalloenzyme. Some remarkable transformations for which no simple analogues exist in small- molecule chemistry under comparable conditions includes the catalytic reduction of N2, to NH3, (nitrogen fixation), the oxidation of water to O2, and the reduction of gem-diols to monoalcohols (reduction of ribonucleotides).Classification of Metalloenzymes is done as per their function. Within each category there are usually several kinds of metal centers that can catalyze the required chemical transformation, a situation analogous to that already encountered for respiratory proteins. The reasons for this diversity are shrouded in evolutionary history, but most likely include bioavailability of a given element in the geosphere biosphere interface during the initial development of a metalloenzyme, as well as pressure to evolve multiple biochemical pathways to secure the viability of critical cellular functions. 5. Communication Roles for Metals in Biology Metal ions are used in biology as triggers for specific cellular functions, and to regulate gene expression. Studies of these cellular communication roles are an exciting frontier area in bioinorganic chemistry. Magnetotactic bacteria use magnetite, Fe3O4, as an internal compass for navigation of the microorganisms. They orient on the Earth's magnetic pole and, when transported to the opposite hemisphere, become disoriented and swim upward. Some bees, homing pigeons, and even humans are also believed to use magnetite in their brains for orientation purposes. Alkali and alkaline earth ions, especially Na+, K+, and Ca2+, are used in biology to trigger cellular responses. The firing of neurons by the rapid influx of sodium ions across the cell membrane and CHEMISTRY Paper No. 15: Bioinorganic Chemistry Module No. 1: Introduction: Bioinorganic Chemistry the regulation of intracellular functions of calcium-binding proteins such as calmodulin are two examples of the phenomenon. In fact, Ca2+ has been referred to as a "second messenger," since primary signals, such as the binding of hormones to the cell surface, are converted into changes in the intracellular concentration of this ion. Among the most recently discovered metal-ion classes in biology are the zinc fingers that occur in many proteins which regulate transcription. 6. Interactions of Metal Ions and Nucleic Acids Metal ions also interact directly with DNA and RNA. Some of these interactions are rather nonspecific, for instance, the stabilization of nucleic-acid structures by Na+ and Mg2+ ions through electrostatic interactions that shield the charged phosphate groups from one another. Recently, more specific binding of metal ions to nucleic acids has been discovered. Thus, Mg2+ and other divalent metal ions serve as cofactors for activating catalytic RNA molecules; and monovalent cations such as K+ stabilize the structure of telomeres, units that terminate the DNA double helix at the ends of chromosomes. The relative stability of these structures may be dictated by the concentrations Na+ and K+ in the cell. Finally, some inorganic-based drugs such as cisplatin act by coordinating directly to DNA and metal complexes have been used as cleaving agents to probe, the tertiary structures of nucleic acids. 7. Metal-Ion Transport and Storage How do metal ions get into cells and how are they stored? This topic is an active area of investigation in bioinorganic chemistry, although it cannot be classified with the others according to metal function. The most thoroughly studied metal in this respect is iron. Iron enters bacterial cells following chelation by low-molecular-weight compounds called siderophores that are excreted by the bacteria. In mammals, iron is bound and transported by the serum protein transferrin, and it is stored by terrain in most life forms. The nearly spherical, hollow shell of this latter protein has the capacity to bind up to 4,500 Fe3+, ions. Details about how iron is passed among these protein systems are incomplete and under active investigation. Copper is transported by the serum protein ceruloplasmin, and another such protein, albumin, is also known to bind and transport metal ions. Metallothionein is a cysteine-rich protein that is expressed in large amounts when excess quantities of certain metal ions, including toxic ones such as Cd2+ or Pb2+, are present in cells. Metallothionein thus serves a protective role and may also be involved in the control of metal transport, storage, and concentration under more normal conditions. 7.1. General aspects of storage and transport of metal-ions Charged Ions must pass through a Hydrophobic Membrane Neutral gases (O2, CO2) and low charge density ions (anions) can move directly through the membrane High charge density cations require help Once inside the cell, metal ions must be transported to the location of their use, then released or stored for later Release from ligand is often not trivial
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