Synthesis, structure and biological activity of nitroxide malonate methanofullerenes

Abstract

study has also revealed some flaws in the previous model of inter-double-helix hydrogen bonding. [1] Imberty, A.; Chanzy, H.; Pérez, S.; Buléon, A.; Tran, V. Functionally substituted fullerene derivatives are of interest since it is possible to obtain both biologically active substances and new materials for nanotechnology on their basis. The spherical platform of fullerene allows one to design molecules with various fragments, which are responsible for the specific properties. At the same time the crystal structure of such compounds is studied insufficiently, that is why Crystallographic Data Bases contain information about not more than 80 fullerene C60 derivatives structures. Interesting feature of these compounds (both derivatives and fullerene complexes) in solid state is their active participation in pi-electronic interactions between each other and with other compounds incorporating aromatic fragments. Owing to these interactions the compounds can form in a crystal the supramolecular structures of various type, that, apparently, finds reflection in their particular properties. Basing on literature structural data for organic derivative of fullerene and on our original X-ray data for the bis-and mono-adducts of the methanofullerenes and pyrrolidino-fullerenes, we have analysed the intermolecular interactions, crystal packing and supramolecular structure of these compounds from the point of view of such interactions. It was found, that in spite of the presence of large substituents in the molecules and solvate molecules in the crystals, which hinder such interactions, the fullerene fragments are closely packed with different fullerene environments-honeycomb structure, zigzag-chain,  dimers, columns and layers, and preferably interact face-to-face with the 5-and 6-membered aromatic rings. The majority of the compounds forms 2D-structures-layers of various topology with fullerenes coordination equal to 3 or 4. Presence of molecules-guests with aromatic fragments or aromatic fragments in the fullerene derivatives leads to their obligatory participation in such interactions and to the destruction of the fullerene-fullerene interactions. Recently we carried out the synthesis of malonate nitroxide metanofullerene, which shows, in combination with known anticancer drug cyclophosphamide, the high antitumor activity against leukemia P-388. It was shown by X-ray single crystal analysis that methanofullerene with two nitroxide groups has a diamond-like environment in the crystal due to fullerene-fullerene interactions [1]. In the same time the first examples of the phosphorylated mono-and bis-methano-fullerenes with large substituents have lower coordination of fragments-zigzag chains and pi-dimers. The comparative analysis of the results for the organic derivatives and for the fullerene C60 inclusion compounds is presented. The topology of the crystals is analysed additionally on the base of proposed model of localization of hydrophilic and hydrophobic regions in the crystals of organic compounds. Keywords: hydrogen...

Structure of surface films of malonate mono- and dinitroxyl methanofullerenes

“…3,4 Dihydroquercetin (DHQ) of 98% purity was obtained from the crushed larch wood (the trademark Bioskan) provided by Rosbioprom Ltd. (Sarov, Nizhny Novgorod Region). Purifica tion of DHQ was carried out by repeated recrystallization from aqueous ethanol (1 : 1) and drying until the weight was constant.…”

“…These results allow us to suggest the nitroxyl methano fullerenes for the in vivo pharmacokinetic studies using ESR spectroscopy and to exclude traditional radioactive and spin labels. 4 To predict behavior of nitroxyl methanofullerenes in living systems, it is of interest to study their physico chem ical properties in two dimensional state in the processes of self organization and structurization in monolayers and surface films at the water-air interface in the presence of various compounds affecting these processes.…”

Catalytic Synergism in a C60IL10TEMPO2Hybrid in the Efficient Oxidation of Alcohols

“…Recently, some C 60 -TEMPO systems have been prepared through Prato, [18] Bamford-Stevens, [19] or Bingel synthetic protocols. [20] In our case, we chose the Bingel-Hirsch protocol [21] in order to prepare the fullerene monoadduct 1 [22] which has been used as starting derivative in the synthesis of the C 60 IL 10 Figure S6). Unfortunately, due to its highly charged nature we were not able to obtain a good mass spectrum of 4.…”

Lupane type triterpenes as structuring elements in the monolayers and films of lecithin and fullerene derivatives

“…Bis nitroxide malonate methanofullerene 4 was synthesized by a reported procedure. 9 Analysis of thin films. The state of monolayers was studied using an automated setup comprising a teflon Langmuir trough (dimen sions 200×137×2 mm), Langmuir balance, and fixed and compress ing barriers.…”

“…7 Bis nitroxide malonate methanofullerene 4 we chose as the lipophilic component exhibit properties of bis and polycenter radical traps in a living organism. 9 It was shown 9 that the combination of the bis nitroxide malo nate methanofullerene with the antitumor drug Cyclo phosphamide demonstrates high activity in tests on ani mals infected with P 388 leukemia.…”