Synthesis and Structure of Novel Copper(II) Complexes with N,O- or N,N-Donors as Radical Scavengers and a Functional Model of the Active Sites in Metalloenzymes.

To evaluate the antioxidant activity of potential synthetic enzyme mimetics, we prepared new five copper(II) complexes via a self-assembly method and named them [Cu(2-(HOCH2)py)3](ClO4)2 (1), [Cu(2-(HOCH2)py)2(H2O)2]SiF6 (2), [Cu2(2-(HOCH2CH2)py)2(2-(OCH2CH2)py)2](ClO4)2 (3), [Cu(pyBIm)3](BF4)2·1.5H2O (4) and [Cu(py2C(OH)2)2](ClO4)2 (5). The synthetic protocol involved N,O- or N,N-donors: 2-(hydroxymethyl)pyridine (2-(HOCH2)py), 2-(hydroxyethyl)pyridine (2-(HOCH2CH2)py), 2-(2-pyridyl)benzimidazole (pyBIm), di(2-pyridyl)ketone (py2CO). The obtained Cu(II) complexes were fully characterised by elemental analysis, FTIR, EPR, UV-Vis, single-crystal X-ray diffraction and Hirshfeld surface analysis. Crystallographic and spectroscopic analyses confirmed chromophores of both monomeric ({CuN3O3} (1), {CuN2O4} (2), {CuN6} (4), {CuN4O2} (5)) and dimeric complex ({CuN2O3} (3)). Most of the obtained species possessed a distorted octahedral environment, except dimer 3, which consisted of two copper centres with square pyramidal geometries. The water-soluble compounds (1, 3 and 5) were selected for biological testing. The results of the study revealed that complex 1 in solutions displayed better radical scavenging activity than complexes 3, 5 and free ligands. Therefore, complex 1 has been selected for further studies to test its activity as an enzyme mimetic. The chosen compound was tested on the erythrocyte lysate of two groups of patients after undergoing chemotherapy and chemoradiotherapy. The effect of the tested compound (1) on enzyme activity levels (TAS, SOD and CAT) suggests that the selected complex can be treated as a functional mimetic of the enzymes.

[The thyroid gland function assessment in women after mastectomy and chemotherapy during breast cancer therapy]. / Ocena funkcji gruczolu tarczowego u kobiet po przebytej mastektomii i chemioterapii raka piersi.

INTRODUCTION: For many years much attention has been focused on an interaction between the breast disease and the thyroid gland function in the literature. In those studies the question whether disease changes in the thyroid gland can induces the breast disease was addressed. On the other hand there are a few works concerning the inverted question whether the breast cancer therapy, in particular after mastectomy and chemotherapy, can disturb the thyroid gland function. The aim of the study is to investigate the influence of the mastectomy and chemotherapy on the thyroid gland function in women after breast cancer therapy. MATERIAL AND METHODS: 173 patients aged 30-80 (average 56) were included in this study. The studied group comprised 97 women after breast cancer therapy (average age 60). The control group consisted of 76 patients (average age 55). 75 patients after mastectomy of the studied group were additionally treated with chemotherapy, but in 22 women chemotherapy was not applied. The following methods were used to carry out the research: the USG method was applied to evaluate thyroid morphological condition in women after mastectomy and chemotherapy; the color Doppler technique was used for dynamic presentation and fine- needle aspiration biopsy: examination of the thyroid functional state by measuring the TSH, fT(3), fT(4) hormone concentration and the level of antithyroid antibodies. RESULTS: An average concentration of antithyroid antibodies: anti-TPO and anti-Tg was found significantly higher in the studied group of women after chemotherapy, comparing with the control group. The level of fT(3) hormone concentration was comparable in all investigated groups. Nevertheless, the average concentration of TSH was found higher in women after mastectomy and chemotherapy and as a consequence leading to hypothyroidism. CONCLUSION: Taking into consideration the high level of the concentration of antithyroid antibodies: (anti-TPO and anti- Tg), which lead to destruction of the thyroid gland tissue, the thyroid gland function of the women after mastectomy and chemotherapy should be monitored morphologically as well as functionally.