ABSTRACT
A new macrocyclic ligand was synthesized by a reaction between diethylenetriaminepentaacetic (DTPA) dianhydride and trans-1,4-diaminocyclohexane, and the Gd(III) and Yb(III) complexes were prepared. The compounds were characterized by spectroscopic methods. Structural calculation by DFT shows that the amide linkages are arranged in such a way that a conformational strain is minimized in the macrocyclic frame. The coordination modes of the ligand and water in the metal complexes were also determined by DFT. The longitudinal relaxation time T1 was measured for aqueous solutions of the Gd(III) complex. The T1 relaxivity arises from the structural feature that a water molecule coordinated to the paramagnetic metal is surrounded by a large open space, through which the exchange of water occurs readily to shorten the relaxation time of water in the entire region, as a result of the chelate conformation defined strictly by the amide groups and the cyclohexane ring.
ABSTRACT
The Cu2+, Mn2+, and Fe3+ complexes of a 14 membered macrocycle were synthesized and their antioxidant capacities were evaluated against ABTS and DPPH radicals, with the objective of collecting insights into the biomimetic role of the central metal ions. The macrocycle, abbreviated as H2L14, is a derivative of EDTA cyclized with 1,4-diamine, and the moderately flexible macrocyclic frame permits the formation of [ML14·H2O] chelates with octahedral coordination geometries common among the metal ions. The metal complexes were characterized by electrospray-ionization mass spectrometry, Fourier transform infrared spectroscopy, and Raman and X-ray photoelectron spectroscopic methods, as well as thermogravimetric analysis; the octahedral coordination geometries with water coordination were optimized by DFT calculations. The antioxidant assays showed that [FeL14·H2O]+ was able to scavenge synthetic radicals with moderate capacity, whereas the other metal chelates did not show significant activity. The Raman spectrum of DPPH in solution suggests that interaction was operative between the Fe3+ chelate and the radical so as to cause scavenging capability. The nature of the central metal ions is a controlling factor for antioxidant capacity, as every metal chelate carries the same coordination geometry.
Subject(s)
Antioxidants/chemical synthesis , Coordination Complexes/chemical synthesis , Edetic Acid/chemistry , Macrocyclic Compounds/chemical synthesis , Antioxidants/chemistry , Coordination Complexes/chemistry , Copper/chemistry , Density Functional Theory , Iron/chemistry , Macrocyclic Compounds/chemistry , Manganese/chemistry , Molecular Structure , Spectrometry, Mass, Electrospray Ionization , Spectroscopy, Fourier Transform Infrared , ThermogravimetryABSTRACT
With the objective of studying the conformational and macrocyclic effects of selected metal chelates on their peroxidase activities, Cu2+ and Fe3+ complexes were synthesized with a macrocyclic derivative of ethylenediaminetetraacetic acid and o-phenylenediamine (abbreviated as edtaodH2) and its new open-chain analogue (edtabzH2). The Fe3+ complex of edtaodH2 has a peroxidase-like activity, whereas the complex of edtabzH2 does not. The X-ray study of the former shows the formation of a dimeric molecule {[Fe(edtaod)]2O} in which each metal with an octahedral coordination is overposed over the macrocyclic cavity, as a result of rigid macrocyclic frame, to form an Fe-O-Fe bridge; the exposure of the central metal to the environment facilitates the capture of oxygen to drive the biomimetic activity. The peroxidase-inactive Fe3+ complex consists of a mononuclear complex ion [Fe(edtabz)(H2O)]+, the metal ion of which is suited in a distorted pentagonal bipyramid to be protected from environmental oxygen. The copper(II) complexes, which have mononuclear structures with high thermodynamic stability compared with the iron(III) complexes, show no peroxidase activity. The steric effects play a fundamental role in the biomimetic activity.
