Mass Spectrometric Evaluation of β-Cyclodextrins as Potential Hosts for Titanocene Dichloride

Bent metallocene dichlorides (Cp2MCl2, M = Ti, Mo, Nb, …) have found interest as anti-cancer drugs in order to overcome the drawbacks associated with platinum-based therapeutics. However, they suffer from poor hydrolytic stability at physiological pH. A promising approach to improve their hydrolytic stability is the formation of host-guest complexes with macrocyclic structures, such as cyclodextrins. In this work, we utilized nanoelectrospray ionization tandem mass spectrometry to probe the interaction of titanocene dichloride with β-cyclodextrin. Unlike the non-covalent binding of phenylalanine and oxaliplatin to β-cyclodextrin, the mixture of titanocene and β-cyclodextrin led to signals assigned as [βCD + Cp2Ti–H]+, indicating a covalent character of the interaction. This finding is supported by titanated cyclodextrin fragment ions occurring from collisional activation. Employing di- and trimethylated β-cyclodextrins as hosts enabled the elucidation of the influence of the cyclodextrin hydroxy groups on the interaction with guest structures. Masking of the hydroxy groups was found to impair the covalent interaction and enabling the encapsulation of the guest structure within the hydrophobic cavity of the cyclodextrin. Findings are further supported by breakdown curves obtained by gas-phase dissociation of the various complexes.

Thermal Properties of Fullerene С56

The behavior of С56 fullerene when heated in a nitrogen atmosphere at a pressure of 105 Pa was studied using computer thermodynamic modeling. The modeling consisted in a complete thermodynamic analysis of the system using the TERRA software package, which is one of the most developed and efficient ones that implements such thermodynamic calculations. Experiment temperature ranges are from 273 to 3373 К. Based on the calculated data, a graph of the carbon balance in the С56-N2 system was constructed, the ongoing physicochemical processes were described, divided into four classes: sublimation, dissociation in the gas phase, chemical reactions occurring in the gas phase, dissociation and chemical reaction in the gas phase. Temperature intervals of reactions are identified. The equilibrium constants of the reactions are calculated and described, as well as the coefficients of these constants are found using the least squares method. The temperature interval of thermal stability of the condensed C56 fullerene and C56 vapors is defined. This work is one of the series of works on the properties of nanoparticles, in the future it is planned to study the thermal properties of higher fullerenes. The data obtained can be used to determine the explosive and fire hazardous properties of fullerenes as a dispersed solid.