Anna Zorkovská

Cystine-capped CdSe@ZnS nanocomposites: mechanochemical synthesis, properties, and the role of capping agent

Cystine-capped CdSe@ZnS nanocomposites were synthesized mechanochemically with the aim to prepare a material which could be used in medicine for biosensing applications. Although synthesized CdSe@ZnS nanocomposites were capped with l-cysteine, cystine was formed from l-cysteine during the milling process. It was proven that water plays the key role in this oxidative transformation. The novel material was characterized by the complex of physico-chemical methods (FTIR, XPS, SEM, EDX, surface area measurements) and CHNS analysis. The leakage of Cd2+ and Zn2+ ions into physiological solution was also studied.

CdS/ZnS nanocomposites: from mechanochemical synthesis to cytotoxicity issues.

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.

Ultrafast mechanochemical synthesis of copper sulfides

Covellite, CuS and chalcocite, Cu2S were prepared within a few seconds by ball milling of the elemental precursors. The morphology of the used copper, related to its preparation method, was found to be the key factor for the ultrafast reaction. The explosive character of the reaction was monitored by the gas pressure changes in the milling vessel and the reaction progress was pursued by X-ray diffraction analysis and Soxhlets extraction. The local temperature at the contact site between the milling media and the milled mixture at the time of explosion was calculated as 950 °C for CuS and 700 °C for Cu2S. The mean crystallite size of the prepared products was 15 nm for CuS and 65 nm for Cu2S.

Preparation, properties and anticancer effects of mixed As4S4/ZnS nanoparticles capped by Poloxamer 407

Arsenic sulfide compounds have a long history of application in a traditional medicine. In recent years, realgar has been studied as a promising drug in cancer treatment. In this study, the arsenic sulfide (As4S4) nanoparticles combined with zinc sulfide (ZnS) ones in different molar ratio have been prepared by a simple mechanochemical route in a planetary mill. The successful synthesis and structural properties were confirmed and followed via X-ray diffraction and high-resolution transmission electron microscopy measurements. The morphology of the particles was studied via scanning electron microscopy and transmission electron microscopy methods and the presence of nanocrystallites was verified. For biological tests, the prepared As4S4/ZnS nanoparticles were further milled in a circulation mill in a water solution of Poloxamer 407 (0.5wt%), in order to cover the particles with this biocompatible copolymer and to obtain stable nanosuspensions with unimodal distribution. The average size of the particles in the nanosuspensions (~120nm) was determined by photon cross-correlation spectroscopy method. Stability of the nanosuspensions was determined via particle size distribution and zeta potential measurements, confirming no physico-chemical changes for several months. Interestingly, with the increasing amount of ZnS in the sample, the stability was improved. The anti-cancer effects were tested on two melanoma cell lines, A375 and Bowes, with promising results, confirming increased efficiency of the samples containing both As4S4 and ZnS nanocrystals.

Mechanochemical synthesis and in vitro studies of chitosan-coated InAs/ZnS mixed nanocrystals

In this paper, InAs/ZnS mixed nanocrystals were synthesized by dry high-energy milling approach in the first step. The obtained nanocrystals were characterized from structural point of view by X-ray diffraction analysis and Raman spectroscopy, and from the morphological point of view by scanning electron microscopy. In the next step, the nanocrystals were subjected to wet ultra-fine milling in order to obtain a nanosuspension of chitosan-coated InAs/ZnS nanocrystals with bio-imaging properties. The stability of the nanosuspension was examined by zeta potential and particle size distribution measurements. The prepared nanosuspension was stable with high values of zeta potential. Its optical properties were also studied using UV–Vis and PL spectroscopies. The determined fluorescent properties confirming the potential in bio-imaging applications were verified on cancer cell lines Caco-2, HCT116, HeLa, and MCF7.