2 research outputs found
Silver(I) and Thioether-bis(pyrazolyl)methane Ligands: The Correlation between Ligand Functionalization and Coordination Polymer Architecture
This
work examines the crystal structures of 15 AgÂ(I) complexes
with thioether functionalized bisÂ(pyrazolyl)Âmethane derivatives to
rationalize the influence of the ligand on the formation of (a) coordination
polymers (CPs), (b) oligonuclear (hexameric and dinuclear) complexes,
and (c) mononuclear complexes. It was previously reported how this
ligand class could generate microporous architectures with permanent
porosity. Some ligand modifications could induce a cavity size modulation
while preserving the same overall architecture. The bisÂ(pyrazolyl)Âmethane
scaffold can be easily functionalized with various structural fragments;
hence the structural outcomes were studied in this work using various
ligand modifications and AgÂ(I) salts. In particular, six new ligand
classes were prepared with the following features: (1) The steric
hindrance on the pyrazole rings L<sup>3,3′Me</sup>, L<sup>5,5′Me</sup>, L<sup>5,3′Me</sup>, L<sup>CF3</sup>, and L<sup>Br</sup> was
modified. (2) The steric hindrance was reduced on the peripheral thioether
group: L<sup>SMe</sup>. (3) Finally, the presence of fluorine and
bromine atoms in L<sup>CF3</sup> and L<sup>Br</sup> offered the possibility
to expand the type of interaction with respect to the ligands based
on hydrocarbon substituents (CH<sub>3</sub>, phenyl, naphthyl). The
effect of the anions was explored using different AgÂ(I) precursors
such as AgPF<sub>6</sub>, AgBF<sub>4</sub>, AgCF<sub>3</sub>SO<sub>3</sub>, or AgNO<sub>3</sub>. A comparison of the crystal structures
allowed for the tentative identification of the type of substituents
able to induce the formation of CPs having permanent porosity to include
a symmetric and moderate steric hindrance on the pyrazolyl moieties
(four CH<sub>3</sub>) and an aromatic and preorganized thioether moiety.
An asymmetric steric hindrance on the pyrazole groups led to the formation
of more varied structural types. Overall, the most frequently reported
structural motifs are the porous hexameric systems and the molecular
chains
Oxidative Stress Induced by Copper and Iron Complexes with 8‑Hydroxyquinoline Derivatives Causes Paraptotic Death of HeLa Cancer Cells
Here,
we report the antiproliferative/cytotoxic properties of 8-hydroxyquinoline
(8-HQ) derivatives on HeLa cells in the presence of transition metal
ions (Cu<sup>2+</sup>, Fe<sup>3+</sup>, Co<sup>2+</sup>, Ni<sup>2+</sup>). Two series of ligands were tested, the arylvinylquinolinic <b>L1–L8</b> and the arylethylenequinolinic <b>L9</b>–<b>L16</b>, which can all interact with metal ions
by virtue of the N,O donor set of 8-HQ; however, only <b>L9</b>–<b>L16</b> are flexible enough to bind the metal in
a multidentate fashion, thus exploiting the additional donor functions. <b>L1</b>–<b>L16</b> were tested for their cytotoxicity
on HeLa cancer cells, both in the absence and in the presence of copper.
Among them, the symmetric <b>L14</b> exhibits the highest differential
activity between the ligand alone (IC<sub>50</sub> = 23.7 ÎĽM)
and its copper complex (IC<sub>50</sub> = 1.8 ÎĽM). This latter,
besides causing a significant reduction of cell viability, is associated
with a considerable accumulation of the metal inside the cells. Metal
accumulation is also observed when the cells are incubated with <b>L14</b> complexed with other late transition metal ions (Fe<sup>3+</sup>, Co<sup>2+</sup>, Ni<sup>2+</sup>), although the biological
response of HeLa cells is different. In fact, while Ni/<b>L14</b> and Co/<b>L14</b> exert a cytostatic effect, both Cu/<b>L14</b> and Fe/<b>L14</b> trigger a caspase-independent
paraptotic process, which results from the induction of a severe oxidative
stress and the unfolded protein response