Eu@C86 isomers: Calculated relative populations

Abstract

Relative populations of four energy-lowest IPR (isolated-pentagon-rule) isomers of Eu@C₈₆ are computed using the Gibbs energy based on characteristics from density functional theory calculations (M06-2X/3-21G?～?SDD entropy term, M06-2X/6-31G*～SDD or B2PLYP(D)/6-31G*～SDD energetics). The calculations confirm that the recently isolated Eu@C₁(7)-C₈₆ species is a major isomer in a relevant temperature region. Relationship to the empty C₈₆ cages is discussed, too.     

Theory of correlations in partly labelled homopolymer melts

Small-angle neutron scattering by a polymer melt with partly tagged chains is considered. When several types of chain (differently labelled) are present in the system a new long-range correlation effect which modifies the scattering spectrum is predicted. This effect will arise because of the chemical polydispersity of the sample. A general formalism is developed to calculate the scattering intensity and is applied to special cases: diblock and triblock chains. It is shown that even a small chemical polydispersity leads to important long-range fluctuations and modifies the scattering spectrum substantially.     

Two Isomers of C60F48: Computed Inter-isomeric Equilibrium

C₆₀F₄₈ has been known to exist in two isomeric forms of D₃ and S₆ symmetries. However, the quantum-chemical calculations have not agreed on their stability order though a near-isoenergetic picture is otherwise always encountered. In order to clarify the situation, the entropy effects are evaluated for synthetic temperatures of about 500K. The entropy evaluations suggest that the D₃ isomer should be more stable in the potential energy by 2.05-2.55 kcal/mol (to which term the ab initio data are closer than the semiempirical ones).     

Binding affinity of fluorochromes and fluorescent proteins to Taxol™ crystals

The ability of Taxol (paclitaxel) to bind and stabilize microtubules is the basis for its use as an anti-mitotic drug as well as an additive for in vivo and in vitro studies of microtubules. The low solubility of Taxol in aqueous solutions, however, facilitates the formation of Taxol crystals that can be decorated with fluorescent tubulin. In cells treated with Taxol, these decorated Taxol crystals may be mistaken for self-assembled tubulin asters when observed with a fluorescent microscope. We confirmed via fluorescent and differential interference contrast microscopy that Taxol crystals can be decorated not only with fluorescent tubulin but also with other fluorescent proteins and fluorochromes without perturbing their morphology. We used theoretical calculations to further investigate Taxol-fluorescent agent interactions. Using computational docking studies we identified a new, potential Taxol binding site within the tubulin dimmer, allowing the interaction between crystalline Taxol and tubulin. Our calculations, however, show that fluorescent tubulin binding to Taxol crystals is more favorable via the fluorochromes covalently linked to the tubulin dimmers, rather than via the new Taxol-binding site, what is in accordance with our experimental data.     

Three-dimensional FE model for calculation of temperature of a thermosensitive disc

An effect of variations of the temperature-dependent thermophysical properties of materials of a pad and a disc on the temperature generated due to friction was studied. A three-dimensional boundary-value problem of heat conduction of the disc heated locally within the contact area by the moving with the constant deceleration heat flux and the intensity proportional to the specific capacity of friction was formulated. An issue was solved numerically using the finite element method (FEM). The experimental dependences curves of the thermal conductivity and the thermal diffusivity on the temperature ranging from 20 to 500 °C indispensable for the calculations were approximated using Chichinadze's methodology. The comparative analysis of temperature values on the contact surface of the disc obtained with and without influence of temperature dependence of the four different pad and the same quantity of the disc materials was carried out. It was demonstrated that apparent temperature differences arose for each friction couple combining temperature-dependent and constant properties of materials, however, the largest observed discrepancy (13.7%) occurred for the disc made of aluminium alloy series Al MMC. Other disc materials i.e. iron alloy series FCD50, cast iron ChNMKh and steel EI-696 revealed relatively equal temperature differences of order of 6.4%. Furthermore incorporated in the formula for the heat partition temperature variability of the thermophysical properties of materials affected the resulting contact temperature of the disc for friction couple combined exclusively with the titanium pad VT-14 (3.1%).     

Studies on some properties of poly(phenylene sulphide)

Poly(phenylene sulphide) was synthesized by a direct method. Benzene and elemental sulphur were used as substrates, and aluminium chloride as a catalyst. The obtained final product was characterized by IR, VIS-UV, wide angle X-ray and mass spectroscopy, thermal, and elemental analyses. On the base of the analytical methods the molecular structure of the obtained polymer was discussed.     

Structure and properties of 6061 + 26 mass% Si aluminum alloy produced via coupled rapid solidification and KOBO-extrusion of powder

Experiments on mechanical consolidation of rapidly solidified (RS) powder of 6061 + 26 mass% Si alloy were performed using the oscillating-die extrusion method. The RS powder was wrapped in thin-wall 6061-alloy cup 35 mm in diameter and vacuum-compressed by means of 100 ton press. Bars 8 mm in diameter were extruded with cross-section reduction of λ = 19 without any preheating of the charge. Tubes with a diameter/wall thickness of 14 mm/1 mm and cross-section reduction of λ = 33 were also manufactured with success. TEM/STEM observations revealed a very fine structure of as-extruded material and bimodal distribution of quasi-spherical silicon particles. Statistical analysis revealed a silicon fine fraction of 0.1–0.7 μm and a coarse fraction 2.1–2.5 μm in diameter. Examination by means of TEM did not reveal any significant changes in the morphology of the silicon particles, even when a high extrusion ratio and the material annealing after deformation were used. Hot compression tests on as-extruded rods (λ = 19) and preliminary annealed samples were performed at a constant true strain rate of 5 × 10^?3 s^?1 within the temperature range of 293–823 K. High strength of the material and relatively high ductility of samples deformed by compression up to ?_t ? 0.4 were observed. The maximum flow stress value for as-extruded material was reduced with deformation temperature from ～390 to ～3.5 MPa for 293 and 823 K, respectively. Annealing of the samples at 773 K/30 min was found to reduce the maximum flow stress by 30–40%. Tensile strengths of similar as-cast alloys and materials manufactured by means of other powder metallurgy methods were shown for the purpose of comparison.