Systematic study of lanthanoid endohedral metallofullerenes: Production yields, HPLC retention time and reactor irradiation effects

We made systematic studies of lanthanoid metallofullerenes on the following three properties using the radiochemical method: (1) the relative production yields of metallofullerene species, (2) variation of the HPLC retention time among M(III)@C₈₂ species, and (3) the effects of the reactor irradiation on the survival yields of each metallofullerene species. The production yields of M@C₈₂ relative to La@C₈₂ were found to decrease as the atomic number of M became larger and as the number of atom ratio, M/C, in the carbon rod became larger. On the other hand, the production yields of M₁M₂@C₈₂, relative to that of LuM@C₈₂ were found to increase for the larger atomic number. The retention time for the M(III)@C₈₂ species in the Buckyprep column was found to become slightly longer for the larger atomic number but it becomes abruptly larger for Gd, and Tb by about 5%. The overall effects of the reactor irradiation on the survival yields (or retention yields) of M@C₈₂ species were found to be (19.7±2.1)%.     

Production and characterization of actinide metallofullerenes

We have, previously, reported on the HPLC elution behavior of the Th, Pa, U, Np, and Am metallofullerenes and the UV/vis/NIR absorption spectra of the Th@C₈₄ and U@C₈₂ species. In this paper, the followings are reported: (1) Pu metallofullerenes were produced and their HPLC elution behavior was investigated using a radiotracer technique. The HPLC chromatogram of this metallofullerene was found to be almost the same as that of the Np and Am metallofullerenes. (2) The oxidation states of Th@C₈₄ and U@C₈₂ produced in macroscopic quantities were examined by XANES (X-ray absorption near edge structure) measurements. The oxidation state of the U atom in the C₈₂ fullerene cage was estimated to be 3+ with the formal charge of the ionic molecule being U³⁺@C₈₂ ^3-.     

On cyclic biquadratic fields related to a problem of Hasse

In this note we shall prove that there exist infinitely many cyclic biquadratic fieldsK whose integral bases are neither {1, , ², } nor {1, , , ³) for any numbers , inK. Next, we shall construct infinitely many cyclic biquadratic fieldsK which have the index 1, but still have not the integral basis {1, , ², ³) for every inK. Finally we shall give a class of biquadratic fields for a problem of Hasse concerning an integral basis.     

Electronic state of Ce@C82

Time-differential perturbed angular correlation method was applied to Ce@C₈₂ in order to investigate the electronic properties of the encaged Ce atom. The nuclear quadrupole frequency of the nuclear spin of the Ce was successfully determined as ω_Q = 6.5(3)·10⁷ rad/s, which is much greater than what has already been estimated for Ce⁴⁺ and La³⁺ in other compounds. By comparing the present value with the values for the Ce⁴⁺ and La³⁺, it was inferred that the valence state of the encaged Ce atom is trivalent.     

Linear viscoelastic behavior of perfluorooctyl sulfonate micelles: effects of counter-ions

Linear viscoelastic behavior was investigated for aqueous solutions of perfluorooctyl sulfonate (C₈F₁₇SO⁻ ₃; abbreviated as FOS) micelles having a mixture of tetraethylammonium (N⁺(C₂H₅)₄; TEA) and lithium (Li⁺) ions as the counter-ions. The solutions had the same FOS concentration (0.1 mol l⁻¹) and various Li⁺ fractions in the counter-ions, φ_Li = 0−0.6, and the FOS micelles in these solutions formed threads which further organized into dendritic networks. At T ≤ 15 °C, the terminal relaxation time τ and the viscosity η, governed by thermal scission of the networks, increased with increasing φ_Li up to 0.55. A further increase of φ_Li resulted in decreases of τ and η and in broadening of the relaxation mode distribution. These rheological changes are discussed in relation to the role of TEA ions in thermal scission: Previous NMR studies revealed that only a fraction of TEA ions were tightly bound to the FOS micellar surfaces and these bound ions stabilized the thread/network structures. The concentration of non-bound TEA ions, C_TEA ^*, decreased and finally vanished on increasing φ_Li up to φ_Li ^* ≅ 0.6, and the concentration of the bound TEA ions significantly decreased on a further increase of φ_Li. The non-bound TEA ions appeared to catalyze the thermal scission of the FOS threads, and the observed increases of τ and η for φ_Li < 0.55 were attributed to the decrease of C_TEA ^*. On the other hand, the decreases of τ and η as well as the broadening of the mode distribution, found for φ_Li > 0.55 (where C_TEA ^* ≅ 0), were related to destabilization of the FOS threads/networks due to a shortage of the bound TEA ions and to the existence of concentrated Li⁺ ions. Viscoelastic data of pure FOSTEA and FOSTEA/FOSLi/TEACl solutions lent support to these arguments for the role of TEA ions in the relaxation of FOSTEA/FOSLi solutions. Received: 12 October 1999/Accepted: 1 November 1999     

Laser ablation of liquid surface in air induced by laser irradiation through liquid medium

The pulse laser ablation of a liquid surface in air when induced by laser irradiation through a liquid medium has been experimentally investigated. A supersonic liquid jet is observed at the liquid–air interface. The liquid surface layer is driven by a plasma plume that is produced by laser ablation at the layer, resulting in a liquid jet. This phenomenon occurs only when an Nd:YAG laser pulse (wavelength: 1064 nm) is focused from the liquid onto air at a low fluence of 20 J/cm². In this case, as Fresnel’s law shows, the incident and reflected electric fields near the liquid surface layer are superposed constructively. In contrast, when the incident laser is focused from air onto the liquid, a liquid jet is produced only at an extremely high fluence, several times larger than that in the former case. The similarities and differences in the liquid jets and atomization processes are studied for several liquid samples, including water, ethanol, and vacuum oil. The laser ablation of the liquid surface is found to depend on the incident laser energy and laser fluence. A pulse laser light source and high-resolution film are required to observe the detailed structure of a liquid jet.     

Anisotropic polymerization of a long-chain diacetylene derivative Langmuir-Blodgett film on a step-bunched SiO2/Si surface

Alternating facet/terrace nanostructures were fabricated on a SiO2 surface by step-bunching and thermal oxidation of a vicinal Si(111) substrate, and their influence upon the polymerization direction of a long-chain diacetylene derivative monolayer film was investigated by angle-dependent polarized near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. It was found that the peak intensity of the C 1s-pi transition was stronger when the electric vector plane of the incident X-ray was parallel to the direction of the periodic facet/terrace structures rather than perpendicular to them. On the contrary, a polymer film fabricated on a flat SiO2 surface showed no in-plane anisotropy of the peak intensity. These results indicate that the diacetylene groups in the diacetylene derivative monolayer are preferentially photopolymerized in the direction not across but along the periodic one-dimensional structures on the step-bunched and thermally oxidized SiO2/Si(111) surface.