Hydrated fullerene C60 (HyFn) is a supramolecular object in which the nanosized fullerene molecule is enclosed in a multilayer shell of water molecules. Despite the fact that fullerene C60 is chemically rather inert, aqueous solutions of HyFn exhibit a wide spectrum of biological activity in particular in low and ultra-low concentrations. Thus, physical and chemical properties of aqueous solutions of HyFn in a wide range of its dilutions are of interest. Here we compared some physical and chemical properties of aqueous systems prepared by successive 100-fold dilutions of HyFn (10–7 M) with deionized water, with their intensive shaking at each stage up to the calculated HyFn concentration of 10–31 M and of the corresponding “dilutions” of deionized water prepared in the same manner (controls). We studied the character of рН changes in dilutions when titrating them with HCl and NaOH. It turned out that HyFn dilutions had significantly higher buffering capacity against acidification with HCl than control water “dilutions.” At the highest acidity reached pH in all HyFn dilutions was almost 0.3 units higher than in the respective controls. Average buffering capacity of HyFn dilutions and water controls when titrated with NaOH did not differ. However, differences in buffering capacity could be seen between consecutive dilutions of HyFn at their titration either with NaOH or with HCl. Most prominent differences were observed between consecutive HyFn dilutions in the range of calculated concentrations 10–17–10–31 M titrated with NaOH while no significant differences in pH between equivalent “dilutions” of control water were observed. Similar though less prominent variations in buffering capacity between consecutive HyFn dilutions titrated with HCl were also noticed. Thus, titration with an acid and especially with an alkali made it possible to reveal differences between individual dilutions of HyFn, as well as differences between HyFn dilutions and corresponding dilutions of water. These features may be due to complexity in the structural properties of aqueous systems, which, supposedly, can arise due to the emergence of heterogenous aqueous regions (“clouds”) in the course of their dilutions with intensive mixing at each stage. In order to find out if such heterogeneity is a characteristic for HyFn dilutions we used the method of drying microsphere-containing droplets, whose aqueous base were either HyFn dilutions in the range of calculated HyFn concentration 10–7–10–31 M or respective water controls. It was found that a significant part of HyFn dilutions is characterized by mesoscopic heterogeneity. It showed up by the tendency of microspheres to concentrate in a specific way resembling ornaments once the droplets had dried. As the degree of HyFn dilution increased, the number of dried droplets with an ornament-like microsphere distribution increased. Same was also observed in water control drops. However, for the dilutions of HyFn equivalent to concentrations 10–19–10–31 M the percentage of complexly structured dried up droplets reached 60–80%, while for dried out drops of respective water controls it did not exceed 15–20%. Thus, the physicochemical properties of high dilutions of hydrated fullerene differ not only from each other dependently on the dilution level, but also from those of high dilutions of water, which can be explained by the structuredness and heterogeneity of these aqueous systems. Therefore, upon dilution process the properties of the solutions change according to complex and non-linear laws so that final dilutions cannot be identical in their properties and features to those of the initial solutions (before dilutions process) and to the untreated water. Dilution process, in view of the aforementioned, should not be underestimated when analyzing properties of the solutions, having shown to be able to affect dramatically properties of the solutions.
Structure and physical properties of silkworm cocoons
