Baláž Peter, Baláž Matej, Dutková Erika, Zorkovská Anna, Kováč Jaroslav, Hronec Pavol, Kováč Jaroslav, Čaplovičová Mária, Mojžiš Ján, Mojžišová Gabriela, Eliyas Alexander, Kostova Nina G
Institute of Geotechnics, Slovak Academy of Sciences, 04001 Košice, Slovakia.
Institute of Geotechnics, Slovak Academy of Sciences, 04001 Košice, Slovakia.
Mater Sci Eng C Mater Biol Appl. 2016 Jan 1;58:1016-23. doi: 10.1016/j.msec.2015.09.040. Epub 2015 Sep 10.
CdS/ZnS nanocomposites have been prepared by a two-step solid-state mechanochemical synthesis. CdS has been prepared from cadmium acetate and sodium sulfide precursors in the first step. The obtained cubic CdS (hawleyite, JCPDS 00-010-0454) was then mixed in the second step with the cubic ZnS (sphalerite, JCPDS 00-005-0566) synthesized mechanochemically from the analogous precursors. The crystallite sizes of the new type CdS/ZnS nanocomposite, calculated based on the XRD data, were 3-4 nm for both phases. The synthesized nanoparticles have been further characterized by high-resolution transmission electron microscopy (HRTEM) and micro-photoluminescence (μPL) spectroscopy. The PL emission peaks in the PL spectra are attributed to the recombination of holes/electrons in the nanocomposites occurring in depth associated with Cd, Zn vacancies and S interstitials. Their photocatalytic activity was also measured. In the photocatalytic activity tests to decolorize Methyl Orange dye aqueous solution, the process is faster and its effectivity is higher when using CdS/ZnS nanocomposite, compared to single phase CdS. Very low cytotoxic activity (high viability) of the cancer cell lines (selected as models of living cells) has been evidenced for CdS/ZnS in comparison with CdS alone. This fact is in a close relationship with Cd(II) ions dissolution tested in a physiological solution. The concentration of cadmium dissolved from CdS/ZnS nanocomposites with variable Cd:Zn ratio was 2.5-5.0 μg.mL(-1), whereas the concentration for pure CdS was much higher - 53 μg.ml(-1). The presence of ZnS in the nanocrystalline composite strongly reduced the release of cadmium into the physiological solution, which simulated the environment in the human body. The obtained CdS/ZnS quantum dots can serve as labeling media and co-agents in future anti-cancer drugs, because of their potential in theranostic applications.
硫化镉/硫化锌纳米复合材料通过两步固态机械化学合成法制备。第一步,由醋酸镉和硫化钠前驱体制备硫化镉。然后,在第二步中,将所得的立方硫化镉(硫镉矿,JCPDS 00 - 010 - 0454)与通过类似前驱体机械化学合成的立方硫化锌(闪锌矿,JCPDS 00 - 005 - 0566)混合。基于X射线衍射(XRD)数据计算得出的新型硫化镉/硫化锌纳米复合材料的两个相的微晶尺寸均为3 - 4纳米。合成的纳米颗粒通过高分辨率透射电子显微镜(HRTEM)和微光致发光(μPL)光谱进行了进一步表征。PL光谱中的PL发射峰归因于纳米复合材料中与镉、锌空位和硫间隙相关的深度处发生的空穴/电子复合。还测量了它们的光催化活性。在光催化活性测试中,用于使甲基橙染料水溶液脱色时,与单相硫化镉相比,使用硫化镉/硫化锌纳米复合材料时该过程更快且效率更高。与单独的硫化镉相比,已证明癌细胞系(选为活细胞模型)对硫化镉/硫化锌具有非常低的细胞毒性活性(高活力)。这一事实与在生理溶液中测试的镉(II)离子溶解密切相关。具有可变镉:锌比的硫化镉/硫化锌纳米复合材料溶解出的镉浓度为2.5 - 5.0μg·mL⁻¹,而纯硫化镉的浓度则高得多 - 53μg·mL⁻¹。纳米晶复合材料中硫化锌的存在极大地减少了镉向生理溶液中的释放,该生理溶液模拟了人体环境。由于其在治疗诊断应用中的潜力,所获得的硫化镉/硫化锌量子点可作为未来抗癌药物中的标记介质和共剂。