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Potentiometric and Speciation Studies on the Complex Formation Reactions of [Pd(2-methylaminomethyl)-pyridine)(H2O)2]2+ with Some Bio-active Ligands and Displacement Reaction of Coordinated Inosine

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Abstract

The stoichiometry and stability constants of the complexes formed between [Pd(MAMP)(H2O)2]2+ and various biologically relevant ligands containing different functional groups were investigated. The ligands used are amino acids, peptides and DNA constituents. The results show the formation of 1:1 complexes with amino acids and peptides and the corresponding deprotonated amide species. Structural effects of peptides on amide deprotonation were investigated. The purine and pyrimidine bases uracil, uridine, cytosine, inosine, inosine 5′-monophosphate (5′-IMP) and thymine form 1:1 and 1:2 complexes. The concentration distribution of the various complex species was calculated as a function of pH. The effect of chloride ion concentration on the formation constant of CBDCA with Pd(MAMP)2+ was also reported. The results show ring opening of CBDCA and monodentate complexation of the DNA constituent with the formation of [Pd(MAMP)(CBDCA-O)DNA], where (CBDCA-O) represents cyclobutane dicarboxylate coordinated by one carboxylate oxygen. The equilibrium constant of the displacement reaction of coordinated inosine, as a typical DNA constituent, by SMC and/or methionine was calculated. The results are expected to contribute to the chemistry of antitumor agents. The calculated parameters of the optimized complexes support the measured formation constants.

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Abbreviations

CBDCA:

1,1-Cyclobutanedicarboxylic acid

MAMP:

2-(Methylamino)methylpyridine

5′-IMP:

Inosine-5′-monophosphate

5′-GMP:

Guanosine-5′-monophosphate

SMC:

S-methyl-l-cysteine

DMEN:

N,N′-Dimethylethylenediamine

Thr:

Threonine

Ser:

Serine

En:

Ethylenediamine

1,3-DAP:

1,3-Diaminopropane

BPY:

N,N′-Bipyridyl

α-Ala:

α-Alanine

β-Ala:

β-Alanine

PM3:

Parametric Method-3

UV:

Ultraviolet

HOMO:

Highest occupied molecular orbital energy

LUMO:

Lowest unoccupied molecular orbital energy

χ:

Mulliken electronegativity

Pi :

Chemical potential

η :

Global hardness

S :

Global softness

ω :

Global electrophilicity

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Authors and Affiliations

  1. Faculty of Science, Chemistry Department, Cairo University, Giza, Egypt

    Abeer T. Abd El-Karim, Islam R. El-Sherif, Wafaa M. Hosny & Ahmed A. El-Sherif

  2. Faculty of Pharmacy, Northern Border University, Rafha, Saudi Arabia

    Eyad K. Alkhadhairi

  3. Faculty of Science, Chemistry Department, King AbdAl-Aziz University, Jeddah, Saudi Arabia

    Mutlaq S. Aljahdali

  4. Faculty of Arts and Science, Chemistry Department, Northern Border University, Rafha, Saudi Arabia

    Ahmed A. El-Sherif

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  1. Abeer T. Abd El-Karim
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  2. Islam R. El-Sherif
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  3. Wafaa M. Hosny
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  4. Eyad K. Alkhadhairi
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  5. Mutlaq S. Aljahdali
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  6. Ahmed A. El-Sherif
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Correspondence to Abeer T. Abd El-Karim or Ahmed A. El-Sherif.

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Abd El-Karim, A.T., El-Sherif, I.R., Hosny, W.M. et al. Potentiometric and Speciation Studies on the Complex Formation Reactions of [Pd(2-methylaminomethyl)-pyridine)(H2O)2]2+ with Some Bio-active Ligands and Displacement Reaction of Coordinated Inosine. J Solution Chem 46, 1024–1047 (2017). https://doi.org/10.1007/s10953-017-0621-z

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