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Two Cu(II)‑Based Coordination Polymers: Photocatalytic Dye Degradation and Thyroid Cancer Activity by Inducing ROS Mediated Cancer Cell Apoptosis Wen‑Jing Zhang1 · Dong‑Yin Li1 · Bing Song1 Received: 22 February 2020 / Accepted: 10 April 2020 © Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract Via using a mixed-ligand method, two novel coordination polymers based on Cu(II) ions as nodes {[Cu(Py2TTz)0.5(2,6ndc)]·(DMF)·(C2H5OH)}n (1, ­Py2TTz = 2,5‐Bis(4‐pyridyl)thiazolo[5,4‐d]thiazole, 2,6-H2ndc = 2,6-naphthalenedicarboxylic acid) and ­[Cu2(2,6-ndc)2(4-bpdb)·(H2O)3·2DMF]n (2, 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene) were prepared under the solvothermal conditions. In addition, complexes 1 and 2 could be applied as a photocatalysts under ultraviolet light, the degradation property of methylene blue is relatively high. In the research of biological function, the protective activity of compound 1 and compound 2 was assessed. First of all, the accumulation of reactive oxygen species (ROS) in thyroid cancer cells was detected by ROS detection kit. Then, Annexin V-FITC/PI method was used to detect the percentage for thyroid cancer cells apoptosis after treated by compound. Keywords  Coordination polymer · Mixed-ligand · Single crystal X-ray · Dye degradation · Thyroid cancer

1 Introduction Thyroid cancer is a most familiar malignant tumor for the system of endocrine [1]. Although the thyroid cancers more than 80% are the well differentiated, the prognosis is ideal through surgery and radiation iodine treatment [2]. However, thyroid tumors are easy to recur, and the disease progresses quickly, which both increase the difficult for treatment. The incidence rate for the thyroid cancer has enhanced rapidly in these few years, and it currently ranks among the top 10 malignant tumors [3]. The "Epidemiology Surveillance and Final Results" in the United States in 2018 shows that new thyroid cancers worldwide are increasing at an average annual rate of 5%. The incidence of thyroid cancer in China has reached 100,000 cases in 2019, and the incidence rate has increased about 5 times compared with 10 years ago [4]. As a unique ordered porous material, the coordination polymers (CPs) have obtained much attention in recent decades [5–9]. In addition to their fascinating structures, the * Bing Song [email protected] 1



Department of General Surgery, Tianjin First Central Hospital, Tianjin, China

intriguing features of CPs give a variety of latent applications, for instance gas separation and adsorption, harmful substance removal and adsorption, photoluminescence, chemical sensor, proton conduction, and so on [10–12]. Nevertheless, the ultimate structure for CPs is hard to control, due to they may be affected via a lot of reasons, containing synthesis approach, organic ligand, solvent, temperature, the center of metal, ratio of reactant, the value of pH, auxiliary ligand, counterion and so on [13–15]. Among many reasons, organic ligands are considered to be the most pivotal one. Their rigidit