Complexation of C60 Fullerene with Aromatic Drugs

The contributions of various physical factors to the energetics of complexation of aromatic drug molecules with C₆₀ fullerene are investigated in terms of the calculated magnitudes of equilibrium complexation constants and the components of the net Gibbs free energy. Models of complexation are developed taking into account the polydisperse nature of fullerene solutions in terms of the continuous or discrete (fractal) aggregation of C₆₀ molecules. Analysis of the energetics has shown that stabilization of the ligand–fullerene complexes in aqueous solution is mainly determined by intermolecular van der Waals interactions and, to lesser extent, by hydrophobic interactions. The results provide a physicochemical basis for a potentially new biotechnological application of fullerenes as modulators of biological activity of aromatic drugs.     

Induced Absorption of C60 and a Water-Soluble C60-Derivative in SiO2 Sol-Gel Matrices

Porous sol-gel glasses, either impregnated with pure C₆₀ or doped with a methanofullerene derivative, have been studied and induced absorption or reverse saturable absorption (RSA) has been observed in both types of solid materials. The samples impregnated by pure C₆₀ mainly contain well-dispersed fullerene molecules. Unlike crystalline films of C₆₀, their absorption dynamics can be well described by a 5-level model, developed for non-interacting C₆₀-molecules in solutions. Methanofullerene samples, on the other hand, show signs of micellar aggregation and therefore RSA dynamics that are influenced by solid state effects. We observe an important decrease of transmission at high fluences for both kinds of samples, a shortened singlet-state lifetime to that observed in solution, but nonetheless, a triplet yield, that cannot be considered as negligible. In the case of pure C₆₀ in a sol-gel matrix, we can explain the faster de-excitation dynamics, relative to behavior in solution, mainly by the absence of stabilizing aromatic solvents and also by the interaction of the amorphous environment with the molecules. Concerning the methanofullerene samples, the acceleration of the de-excitation dynamics can be principally attributed to solid-state effects due to the micellar aggregation.     

Physicochemical properties of Water-Soluble Fullerene C60-Carbohydrate Composites

Water-soluble composites of fullerene C60 with carbohydrates (saccharose, fructose, and dextrans) prepared by the mechanochemical procedure were analyzed by electronic absorption and ¹³C NMR spectroscopy, thin-layer chromatography, and differential scanning calorimetry.     

Complexation of Fullerene C60 with Various Aromatic Donors

Complexation of fullerene C₆0 with aromatic donors in CCl₄ and decalin was studied spectrophotometrically in the visible and near UV range, and the equilibrium constants were determined.     

Supramolecular Complexation Behavior of Novel Cyclotriveratrylene Derivatives with Benzoate Pendants with C60

Four novel cyclotriveratrylene (CTV) derivatives with three benzoate pendants bearing different aliphatic chains have been prepared in good yields, starting from CTV. The complexation behavior of these CTV derivatives towards C₆₀ in arene solvents has been measured by UV‐visible spectroscopy and high complexation constants are obtained. It is observed that the complexation is promoted pronouncedly by introducing methyl ester groups to the aromatic pendants, while this promoting effect is reduced when the methyl groups are replaced by longer alkyl groups.     

Extraction Equilibria in the Fullerene C60-Fullerene C70-Solvent Systems

A new method was proposed for separation of light fullerenes C₆₀ and C₇₀ based on realization of two-phase extraction equilibria in multicomponent fullerene-containing systems C₆₀-C₇₀-solvent I-solvent II and C₆₀-C₇₀-solvent I-solvent II-inert component. The principal possibility and high efficiency of the extraction separation of light fullerenes were demonstrated.     

Synthesis of Some Selenacrown Ethers and the Thermodynamic Origin of Their Complexation with C60

Two new selenacrown ethers, i.e., N,N′-dimethyl-1,11-diaza-4,8,14,18,-tetraselenacycloicosane (1) and 7,11-diseleno-2,3,15,16,-dibenzo-1,4,14,17,20,23-hexaoxacyclopentacosane (2), have been synthesized and characterized by elemental analysis and UV, and ¹H-NMR spectroscopy. An X-ray crystallographic structure was obtained for 1. UV-spectrophotometric titrations have been performed in CCl₄ solution at 25–50 °C to obtain the complex stability constants (K_s) and the thermodynamic parameters (ΔH⁰ and TΔS⁰) for the stoichiometric 1:1 complexation of [60]-fullerene (C60) with the crown ethers 1–4. The obtained K_s values together with that reported for dicyclohexano-24-crown-8 (5) reveal that, the more the heteroatom numbers in crown ether ring are, and the larger the cavity sizes of crown ethers are, the higher theK_svalues for complexation with C60 are. Thermodynamically, the complexation of C60 with 1–5 is absolutely enthalpy-driven in CCl₄, while the complex stability is governed by the entropy term.     

Fluorescent Bis-Calix[4]arene-Carbazole Conjugates: Synthesis and Inclusion Complexation Studies with Fullerenes C60 and C70

Supramolecular chemistry has become a central theme in chemical and biological sciences over the last decades. Supramolecular structures are being increasingly used in biomedical applications, particularly in devices requiring specific stimuli-responsiveness. Fullerenes, and supramolecular assemblies thereof, have gained great visibility in biomedical sciences and engineering. Sensitive and selective methods are required for the study of their inclusion in complexes in various application fields. With this in mind, two new fluorescent bis-calix[4]arene-carbazole conjugates (4 and 5) have been designed. Herein, their synthesis and ability to behave as specific hosts for fullerenes C₆₀ and C₇₀ is described. The optical properties of the novel compounds and their complexes with C₆₀ and C₇₀ were thoroughly studied by UV-Vis and steady-state and time-resolved fluorescence spectroscopies. The association constants (K_a) for the complexation of C₆₀ and C₇₀ by 4 and 5 were determined by fluorescence techniques. A higher stability was found for the C₇₀@4 supramolecule (K_a = 5.6 × 10⁴ M⁻¹; ΔG = −6.48 kcal/mol). Evidence for the formation of true inclusion complexes between the host 4 and C₆₀/C₇₀ was obtained from NMR spectroscopy performed at low temperatures. The experimental findings were fully corroborated by density functional theory (DFT) models performed on the host–guest assemblies (C₆₀@4 and C₇₀@4).     

水溶性C60衍生物的合成及其生物活性

综述近年在水溶性Ｃ_（６０）衍生物合成及生物活性方面所取得的进展。     

Photochemical Preparation of Highly Water-Soluble Pendant [60]Fullerene-Aminopolymers

Abstract— In order to introduce fullerene cages into an aqueous environment, pendant [60]fullerene-poly(propionylethyle-neimine-co-ethyleneimine) was prepared photochemical-ly. The pendant polymer is highly water soluble, with equivalent aqueous solubilities of the polymer-bound [60]fullerene much higher than the solubility of [60]ful-lerene in toluene. The photochemical reaction between [60]fullerene and secondary amine moieties in the ami-nopolymers likely follows a photoinduced electron transfer-proton transfer mechanism. The pendant polymer structures, which are represented by dehydrogenated di-and tetra-aminofullerene linkages, were characterized by use of proton and 13C NMR, Fourier transform-infrared spectroscopy, gel-permeation chromatography and optical spectroscopic methods.     

Positron annihilation in C60 and K6C60

The positron density distributions in C₆₀ and K₆C₆₀ have been evaluated using the positron lifetime and Doppler-broadening spectroscopy for the annihilation radiation.In C₆₀, positrons are distributed in the interstitial sites between the C₆₀ molecules,which has been demonstrated by measurements of the temperature dependence of the Doppler-broadening of the annihilation radiation. On the other hand, the positron density distribution must be greatly changed in K₆C₆₀, because positrons are repelled by Coulomb interactions by the positively charged K atoms. It has been observed that there is an extremely short lifetime and a small Doppler-broadening component for the positron annihilation in K₆C₆₀. This component is considered to reflect the positron annihilation inside a C₆₀ molecule.     

Exohedral Complexation of B40, C60 and Arenes with Transition Metals: A Comparative DFT Study

Holes are inevitable in borospherenes. The surface topography of B₄₀ and its π MOs isolobal to benzene allow for better η⁷‐, η⁶‐ and η³‐ exohedral complexation with transition metal fragments than it is possible with C₆₀ and arenes. η⁷‐complexes of B₄₀ is lower in energy than the η⁶‐complexes for metal fragments such as C₅H₅Mn, C₄H₄Fe, and C₃H₃Co that have relatively diffuse frontier orbitals. The fragment C₆H₆Cr prefers η⁶‐coordination. Near‐isodesmic equations based on density functional theory computations of the transition metal complexes of B₄₀, C₆₀ and C₆H₆ support these anticipations. Transition metal complexation increases the stability of B₄₀.     

Triptycene‐Derived Calix[6]arenes: Synthesis,Structures, and Their Complexation with Fullerenes C60 and C70

Two pairs of novel triptycene‐derived calix[6]arenes 4 a , b and 5 a , b have been efficiently synthesized through both one‐pot and two‐step fragment‐coupling strategies starting from 2,7‐bis(hydroxymethyl)‐1,8‐dimethoxytriptycene 1 . Subsequent demethylation of 4 a , b and 5 a , b with BBr₃ in dry dichloromethane gave the macrocyclic compounds 6 a , b and 7 a , b . Treatment of either 4 a or 6 a with AlCl₃ resulted in the same debutylated product 8 , while 9 was similarly obtained from either 5 a or 7 a . Structural studies revealed that all of the macrocycles have well‐defined structures with fixed conformations both in solution and in the solid state owing to the introduction of the triptycene moiety with a rigid three‐dimensional (3D) structure, making them very different from their classical calix[6]arene counterparts. As a consequence, it was found that all of these the triptycene‐derived calix[6]arenes could encapsulate small neutral molecules in their cavities in the solid state. Moreover, it was also found that the macrocycles 4 b and 5 b showed highly efficient complexation abilities toward fullerenes C₆₀ and C₇₀, forming 1:1 complexes with association constants ranging from (5.22±0.20)×10⁴ to (8.68±0.30)×10⁴ M ^?1.     

Atomic Force Microscopic Investigations of Fibrils Formed by Complexation of Monochelic Polystyrenic Porphyrin and PEGylated Fullerene (C60)

Atomic force microscopic studies have been conducted for insight into the morphological aspects of monochelic porphyrin and fullerene complexes forming fibrils of continuous nature. Alternating dark and bright segments could be envisioned clearly, as individual porphyrin-fullerene repeating units. These fibrils also caused a remarkable red shift in the soret band absorption of porphyrin. Dynamic light scattering analysis was also conducted under different solvent conditions, which showed the swelling of fibrils when the solvent was changed from THF to water.     

Rotation dynamics of C60 molecules in organic superconductor K3C60

The rotation dynamics of C₆₀ molecules in organic superconductor K₃C₆₀ has been investigated from the viewpoint of intramolecular interaction. It is determined that the rotation of C₆₀ at mom temperature has been frozen up within a small region of rotation angle (0°–50°), and pointed out that the reason for the freeze is the physical interaction rather than the geometrical hindrance. The computations of the interactions for alkali-doped compounds A_3-x A′ _x C₆₀ (x = 1, 2, 3; A, A′ = K, Rb, Cs) other than K₃C₆₀ have also been camed out. Fmm the obtained results, it is seen that the superconducting transition temperatures T, are strongly connected with the interactions in them, and this observation is consistent with the discovery of the correlation between T_c, and lattice constants a. Project supported by the National Natural Science Foundation of China.