Self-assembly in systems based on L-cysteine-silver-nitrate aqueous solution: multiscale computer simulation.

We use fully atomistic, quantum mechanics and mesoscopic simulations to investigate multiscale structure formation in a supramolecular system based on aqueous solutions of silver nitrate with L-cysteine (CSS). Fully atomistic modeling reveals that silver mercaptide clusters are formed in solution at the stage of aging, which has a pronounced "core-shell" structure. The core is formed due to the bonding of SAg groups of silver mercaptide (SM) zwitterions while the shell consists of NH3+ and C(O)O- groups. Self-assembly of large-scale aggregates in CSS occurs due to the interaction of SM functional groups located on the surface of the clusters, which allows them to be considered supramonomers. Quantum-mechanical calculations reveal additional insight into the intermolecular interaction of L-cysteine with the components of the system. The data on the structure and properties of supramonomers are used to develop and parameterize a mesoscopic CSS model supplemented with allowance for salt concentration. In the mesoscopic model, supramonomers are presented as "sticky spheres", the interaction between which is determined by short-range and screened Coulomb potentials. Depending on the salt concentration, all structural transitions typical of CSS are observed: the formation of a stabilized colloidal dispersion, the filamentary aggregates of a gel network, the formation of large-scale unbound aggregates, and precipitation. These stages qualitatively reproduce the experimentally observed behavior of a real solution.

L-Cysteine as a reducing/capping/gel-forming agent for the preparation of silver nanoparticle composites with anticancer properties.

The present article reports the in situ preparation of silver nanoparticles (AgNPs) homogeneously distributed in the gel matrix formed using only L-cysteine (CYS) as a bio-reducing agent. The physicochemical methods of analysis confirmed the formation of a gel-network from aggregates consisting of spherical/elliptical cystine-stabilized AgNPs (core) and cysteine/Ag+ complexes (shell) regardless of the used silver salt - AgNO3, AgNO2 or AgOOCCH3. CYS/AgNO3 and CYS/AgOOCCH3 aqueous solution systems needed the addition of electrolytes (Cl- and SO42-) for the gelation process, but the gel-formation in CYS/AgNO2 occurred in one stage without any additional components. The AgNP sizes were about 1-5 nm in diameter for CYS/AgNO3, 5-10 nm for CYS/AgOOCCH3 and 20-40 nm for CYS/AgNO2 systems. The zeta-potential values varied from +60 mV for CYS/AgNO3 to +25 mV for the CYS/AgNO2 system. The MTT-test showed that the obtained composites suppressed the MCF-7 breast cancer cells and the CYS/AgNO3 system possessed the highest activity. Flow cytofluorimetry confirmed that the cell death occurred by apoptosis and this effect was the strongest for the CYS/AgNO3 system. All systems were non-toxic to fibroblast cells. The novel simplest "green chemistry" approach, combining the knowledge of organic, inorganic, physical and supramolecular chemistry could open possibilities for the creation of the newest soft gel materials used in various fields of our life.

L-Cysteine/AgNO2 low molecular weight gelators: self-assembly and suppression of MCF-7 breast cancer cells.

We report a new supramolecular hydrogel based on simple amino acids and silver salt compounds with low molecular weights. The in situ formation of silver nanoparticles during the self-assembly process endows the hydrogel with high cytotoxicity towards adenocarcinoma breast cells but no toxic effects towards embryonic fibroblasts.

Mechanism of gelation in low-concentration aqueous solutions of silver nitrate with l-cysteine and its derivatives.

We discuss the results of experimental studies of the processes of gelation in aqueous solutions of silver nitrate with l-cysteine and its derivatives. We focus on understanding what determines if these small molecules will self-assemble in water at their extremely low concentration to form a gel. A mechanism of gel formation in a cysteine-silver solution (CSS) is proposed. The analysis of the results indicates that filamentary aggregates of a gel network are formed via interaction of NH3+ and C(O)O- groups that belong to neighboring silver mercaptide (SM) aggregates. In turn, formation of sulphur-silver bonds between silver mercaptide molecules is responsible for self-assembling these molecules into SM aggregates which can be considered as supramonomers. Free polar groups located on the surfaces of the aggregates can form hydrogen bonds with water molecules, which explains the unique ability of CSS hydrogels to trap water at low concentrations of low-molecular-weight hydrogelators.