NUCLEOPHILIC SUBSTITUTION REACTIONS OF THE CAFFEINE- DERIVED PT(II) AND PD(II) COMPLEXES WITH IMPORTANT BIOMOLECULES

2021 ◽  
Author(s):  
Snežana Jovanović-Stević ◽  
◽  
Jovana Bogojeski ◽  
A. Caković ◽  
B. Petrović

The application of transition metal complexes as chemotherapeutics has been presented throughout the history. Platinum-based drugs are widely used as anticancer agents with a broad range of antitumor activities. The study of the substitution reactions of metal complexes with nitrogen containing biomolecules can help to develop new antitumor drugs with improved characteristics. Kinetics of the substitution reactions of [Pt(caffeine)2Cl2] and [Pd(caffeine)2Cl2] (caffeine = 1,3,7-trimethylxanthine) complexes with biologically important ligands such as 9-methylguanine (9-MetGua) and guanosine-5’-monophosphate (5’-GMP) were studied by UV-Vis spectrophotometry and by stopped-flow technique. Kinetics measurements were performed under the pseudo-first order conditions at 37 °C and pH = 7.2 (25 mM Hepes buffer) in addition of 50 mM NaCl. The obtained results showed that all substitution reactions undergo the two reaction steps giving the [M(caffeine)2(Nu)2] (M = Pd(II) or Pt(II) and Nu = 5′-GMP or 9-MetGua) as the reaction product. Additionally, [Pd(caffeine)2Cl2] complex was more reactive compared to analogue platinum-complex, while 9-MetGua reacted faster than 5’-GMP.

2020 ◽  
Vol 26 (41) ◽  
pp. 7452-7475 ◽  
Author(s):  
Marta A. Andrade ◽  
Luísa M.D.R.S. Martins

: The development of safe and effective chemotherapeutic agents is one of the uppermost priorities and challenges of medicinal chemistry and new transition metal complexes are being continuously designed and tested as anticancer agents. Scorpionate ligands have played a great role in coordination chemistry, since their discovery by Trofimenko in the late 1960s, with significant contributions in the fields of catalysis and bioinorganic chemistry. Scorpionate metal complexes have also shown interesting anticancer properties, and herein, the most recent (last decade) and relevant scorpionate complexes reported for application in medicinal chemistry as chemotherapeutic agents are reviewed. The current progress on the anticancer properties of transition metal complexes bearing homo- or hetero- scorpionate ligands, derived from bis- or tris-(pyrazol-1-yl)-borate or -methane moieties is highlighted.


2009 ◽  
Vol 74 (1) ◽  
pp. 43-55 ◽  
Author(s):  
Dennis N. Kevill ◽  
Byoung-Chun Park ◽  
Jin Burm Kyong

The kinetics of nucleophilic substitution reactions of 1-(phenoxycarbonyl)pyridinium ions, prepared with the essentially non-nucleophilic/non-basic fluoroborate as the counterion, have been studied using up to 1.60 M methanol in acetonitrile as solvent and under solvolytic conditions in 2,2,2-trifluoroethan-1-ol (TFE) and its mixtures with water. Under the non- solvolytic conditions, the parent and three pyridine-ring-substituted derivatives were studied. Both second-order (first-order in methanol) and third-order (second-order in methanol) kinetic contributions were observed. In the solvolysis studies, since solvent ionizing power values were almost constant over the range of aqueous TFE studied, a Grunwald–Winstein equation treatment of the specific rates of solvolysis for the parent and the 4-methoxy derivative could be carried out in terms of variations in solvent nucleophilicity, and an appreciable sensitivity to changes in solvent nucleophilicity was found.


2010 ◽  
Vol 104 (4) ◽  
pp. 379-384 ◽  
Author(s):  
Xiang Chen ◽  
Li-Jun Tang ◽  
Yu-Na Sun ◽  
Pei-Hong Qiu ◽  
Guang Liang

Sign in / Sign up

Export Citation Format

Share Document