Livre de Lyon Academic Works of Livre de Lyon Science and Mathematical Science 2019 Application of The Principle of Hard and Soft Acids and Bases to Mechanisms of Bioinorganic Reactions -Monograph- Tanja V. Soldatović Novi Pazar State University, Serbia, [email protected] Follow this and additional works at: https://academicworks.livredelyon.com/sci_math Part of the Inorganic Chemistry Commons, Materials Chemistry Commons, Medicinal-Pharmaceutical Chemistry Commons, and the Organic Chemistry Commons Recommended Citation Soldatović, Tanja V., "Application of The Principle of Hard and Soft Acids and Bases to Mechanisms of Bioinorganic Reactions -Monograph-" (2019). Science and Mathematical Science. 5. https://academicworks.livredelyon.com/sci_math/5 This Book is brought to you for free and open access by Livre de Lyon, an international publisher specializing in academic books and journals. Browse more titles on Academic Works of Livre de Lyon, hosted on Digital Commons, an Elsevier platform. For more information, please contact [email protected]. M O In this monograph selected results from this field have been N reported, considering the high velocity of developments. I hope O this monograph will help the researchers and will be catalytic G for the students to join research groups which are motivated R and engaged in discovery of new knowledges which contribute A P to expansion of bioinorganic chemistry fields. H T A N J A V . S TANJA V. SOLDATOVIĆ O L D A T O M O N O G R A P H V I Ć Tanja V. Soldatović APPLICATION OF THE PRINCIPLE OF HARD AND SOFT ACIDS AND BASES TO MECHANISMS OF BIOINORGANIC REACTIONS -MONOGRAPH- Lyon 2019 Author • Tanja V. Soldatović Editor in Chief • Caroline Justet Reviewers Prof. em. Dr. Dr. h. c. mult. Rudi van Eldik Prof. Dr. Basam M. Alzoubi Prof. Dr. Mohamed M. Shoukry Cover Design • Betul Akyar First Edition• © May 2019 ISBN: 978-2-490773-02-2 © copyright All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by an means, electronic, mechanical, photocopying, recording, or otherwise, without the publisher’s permission. Publisher Livre de Lyon Adress: 37 rue marietton, 69009, Lyon France Phone: +330605595613 website: http://www.livredelyon.com e-mail: [email protected] Dr. Tanja V. Soldatović Associate Professor Deaprtment of Chemical-Technological Sciences, State University of Novi Pazar APPLICATION OF THE PRINCIPLE OF HARD AND SOFT ACIDS AND BASES TO MECHANISMS OF BIOINORGANIC REACTIONS Reviewers: Prof. em. Dr. Dr. h. c. mult. Rudi van Eldik Emeritus Professor of Inorganic Chemistry, University of Erlangen-Nuremberg, Germany Professor of Inorganic Chemistry, Jagiellonian University, Krakow, Poland Professor of Inorganic Chemistry, N. Copernicus University, Torun, Poland Prof. Dr. Basam M. Alzoubi Professor of Physical Chemistry, AlBalqa Applied University, AlSalt, Jordan Professor of Physical Chemistry Al-Huson University College, Alhuson, Jordan Prof. Dr. Mohamed M. Shoukry Professor of Inorganic Chemistry. Department of Chemistry. Faculty of Science, Cairo University, Egypt Published by Livre de Lyon Dr. Tanja Soldatović anja Soldatović is associate professor at Department of Chemical-Technological Sciences, State University of TNovi Pazar. Her research field is bioinorganic and medicinal inorganic chemistry (studies related to the biological activity and medical application of transition metal anti-tumour complexes). Currently, her research is focused on zinc and copper complexes. Dr. Tanja Soldatović is author and coauthor of more of 30 peer reviewed articles and two books. She participated in the realization of national scientific research project and international DAAD project. She was a research fellow at University of Sassari, Department of Chemistry, Sassari-Italy and University of Erlangen- Nürnberg, Inorganic Chemistry, Department of Chemistry and Pharmacy, Erlangen-Germany. Dr. Tanja Soldatović is member of professional societies: Serbian Chemical Society, Association for Cancer Research (Serbia) and European Association of Cancer Research. PREFACE It is well known that metal ions play an important role in the biological and biomedical processes. Many processes such as breathing, metabolism, photosynthesis, growth, reproduction, muscle contraction cannot be imagined without the presence of some metal ions. Bioinorganic chemistry, among other thing, is focused on mechanism of biological processes in the organism that occur during applications of essential and non-essential element’s compounds in medicine. Many metal-based coordination compounds are widely used in medicine for the treatment of many diseases, including various cancers, Alzheimer's disease, diabetes, rheumatoid arthritis, etc. In this monograph, the influence of HSAB principle on preference of central metal ions to biologically relevant molecule has been discussed. Taking into account the author’s scientific work on investigations the kinetics and mechanism of interaction between transition metal-based compounds with potential antitumor activity, such as Pt(II), Pd(II) (soft acids) and Zn(II) and Cu(II) (intermediate acids) and biomolecules, a review of the scientific results in this field has been made. Author for more than two decades, investigate substitution processes of monofunctional, bifunctional and dinuclear complexes of platinum(II), palladium(II), lately, zinc(II) and copper(II) with biologically relevant nucleophiles. In this monograph selected results from this field have been reported, considering the high velocity of developments. I hope this monograph will help the researchers and will be catalytic for the students to join research groups which are motivated and engaged in discovery of new knowledges which contribute to expansion of bioinorganic chemistry fields. Novi Pazar, Author May 2019. Abbreviations: D - dissociative mechanisms A - associative mechanisms I - interchange mechanisms k - second-order rate constant H° - standard enthalpy of reaction H - enthalpy of activation S - entropy of activation G - Gibbs energy of activation V - volume of activation - acid dissociation constant K a - pseudo-first order rate constant kobs k - solvolysis rate constants or second-order rate constant 1 - second-order rate constant for direct nucleophilic k2 substitution - anation rate constant k-1 cisplatin - cis-diamminedichloridoplatinum(II) - cis-diamminedichloridoplatinum(II) cis-DDP CDDP - cis-diamminedichloridoplatinum(II) transplatin - trans-diamminedichloridoplatinum(II) - 1,1-cyclobutanedicarboxylate CBDC carboplatin - cis-diammine(1,1- cyclobutanedicarboxylate)platinum(II) nedaplatin - cis-diammineglicolatoplatinum(II) - 2,2-bis-(aminomethyl)-1,3-propanediol zeniplatin (1,1-cyclobutanedicarboxylato)platinum(II) enloplatin - tetrahydro-4H-pyran-4,4-dimetanamine (1,1-cyclobutanedicarboxylato)platinum(II) - 2-methyl-1,4-butanediamine CI-973 (1,1-cyclobutanedicarboxylato)platinum(II) BBR3464 - triplatin tetranitrate - 1,2-diaminocyclohexane dach DNA - deoxyribonucleic acid 5’-GMP - guanosine-5'-monophosphate - adenosine-5'-monophosphatesfat 5’-AMP - guanosine GUO INO - inosine 5’-IMP - inosine-5'-monophosphate - thiol RSH - S-methyl-thioether R-SCH3 DDTC - diethyldithiocarbamate AMP - adenosine- monophosphate ADP - adenosine- diphosphate ATP - adenosine- triphosphate 1,2-d(GpG) - 1,2-guanylyl(3’- 5’)guanosine 1,2-d(ApG) - 1,2-adenosyl(3’- 5’)guanosine 1,3-d(GpG) - 1,3-guanylyl(3’- 5’)guanosine SDS - sodium dodecyl sulfate Tu - thiourea DL-asp - DL-aspartic acid L-met - L-methionine L-cis - L-cysteine gly - glycine GSH - glutathione (-glutamyl-cysteinyl-glycine) GSMe - S-methyl-glutatihione en - 1,2-diamnoethane or ethylenediamine DMSO - dimethylsulfoxide bipy - bipyiridine dien - diethylentriamine (1,5-diamino-3-azapentane) kaq - hydrolysis rate constants terpy - 2,2′:6′,2′′- terpyridine Hepes buffer - 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid PBS buffer - phosphate buffer A - absorption λ - wavelength (nm) t - time (s) UV-Vis - ultraviolet and visible spectroscopy NMR - nuclear magnetic resonance spectroscopy EPR - electron paramagnetic resonance MS - mass spectrometry DFT - density functional theory HPLC - high-performance liquid chromatography MALDI-TOF MS - matrix assisted laser desorption/ionization-time of flight mass spectrometry HPLC-MS - high-performance liquid chromatography-mass spectrometry CONTENTS INTRODUCTION 9 1. TRANSITION METAL ION CHEMISTRY 13 13 1.1. Lewis acid character 1.2. Mechanisms of substitution reactions 16 1.3. Characteristics of the various mechanisms 19 1.4. Bioinorganic reaction mechanism 20 2. PLATINUM-BASED ANTICANCER AGENTS 23 2.1. Mechanism of interactions of anticancer platinum drugas 25 with biomolecules 2.2. Interactions of model monofunctional platinum(II) and 30 palladium(II) complexes with sulfur- and nitrogen donor biomolecules 2.3. Interactions of model bifunctional platinum(II) complexes 42 with sulfur and nitrogen donor biomolecules 2.4. Interactions of dinuclear platinum(II) complexes with sulfur 62 and nitrogen donor biomolecules 3. BIOINORGANIC INTERACTIONS OF ZINC(II) 79 AND COPPER(II) COMPLEXES IN CORRELATION WITH HSAB PRINCIPLE 3.1. Interactions of zinc(II) complexes with biomolecules in 82 correlation with HSAB principle 3.2. Cytotoxic activity of zinc(II) complexes 98 3.2. Interactions of copper(II) complexes with biomolecules in 101 correlation with HSAB principle CONCLUSION 109 REFERENCES 113 INTRODUCTION Bioinorganic chemistry is an interdisciplinary field, examines