Promising Approaches for Determination of Copper Ions in Biological Systems

  • PDF / 2,712,578 Bytes
  • 14 Pages / 612 x 792 pts (letter) Page_size
  • 1 Downloads / 202 Views




Promising Approaches for Determination of Copper Ions in Biological Systems R. V. Timoshenkoa, *, A. N. Vaneeva, b, N. A. Savina, N. L. Klyachkob, Yu. N. Parkhomenkoa, S. V. Salikhova, A. G. Majougaa, b, P. V. Gorelkina, and A. S. Erofeeva, b a National

University of Science and Technology MISiS, Moscow, Russia b Moscow State University, Moscow, Russia *e-mail: [email protected]

Received May 4, 2020; revised June 1, 2020; accepted June 2, 2020

Abstract—In this review, we present and categorize modern analytical methods for quantitative determination of copper mostly aimed at the possibility or prospect of their use in biological systems. We perform a comparative analysis of spectroscopic, electrochemical, and fluorescent methods on the basis of key criteria such as limit of detection, the possibility for in vivo/in vitro application, and the possibility of dynamic real-time measurements. DOI: 10.1134/S1995078020020196

CONTENTS 1. Role of copper in living organisms 1.1. Copper in biochemical processes 1.2. Disruption of copper metabolism in the body 1.3. Copper-based drugs 2. Quantitative assays for copper ions in biological systems 2.1. Spectroscopic and spectrometrical analytical methods 2.2. Microcantilever-based sensors 2.3. Transistor-based sensors 2.4. Chemosensors 2.5. Electrochemical techniques 2.6. Nanocapillary- and nanopore-based sensors Conclusions 1. ROLE OF COPPER IN LIVING ORGANISMS 1.1. Copper in Biochemical Processes In the human body, copper is the third most abundant microelement, after iron and zinc [1]. In the human adult body, the copper content varies in the range of 75 to 100 mg [2]. The major fraction of copper is found in the skeleton and bone marrow (~46 mg), skeletal muscles (~26 mg), liver (~10 mg), brain (~8.8 mg), and blood (~6 mg) [3–5]. A considerable number of enzymes involved in metabolic activity can function properly owing to the presence of copper ions [6]. Copper ions take part in the formation of hemoglobin, melanin, myelin, and thyroxine and are constituents of enzymes such as lysyl oxidaze, ceruloplas-

min, superoxide dismutase, and cytochrome c-oxidase, to name a few [7, 8]. Copper ions in biological systems can function as anti- or prooxidants, depending on their charge state [9, 10]. In the human body, copper occurs mostly in two forms—Cu+ (the reduced form) and Cu2+ (the oxidized form)—and gives rise to numerous complexes with both organic and inorganic ligands [11, 12]. 1.2. Disruption of Copper Metabolism in the Body Apart from ensuring functioning of vital processes in the body, copper ions can trigger undesirable reactions, e.g., redox interactions between reactive oxygen species (ROS), with hydrogen peroxide (H2O2) and the superoxide radical (O2− ) being the most common of these. Haber and Weiss [13] were first to describe the reaction between hydrogen peroxide and superoxide in the presence of transition metals, including copper ions: 3+



Fe / Fe or Cu O2− + H2O2 ⎯⎯⎯⎯⎯⎯⎯ →  O2 +  OH +  OH−.


This reaction gives rise to highly reactive hy