Facile deposition of [60]fullerene on the electrode by electrochemical oxidative polymerization of thiophene

It was found that [60]fullerene encapsulated in anionic calix[8]arenes can be readily deposited by electrochemical oxidative polymerization of ethylenedioxythiophene: the resultant electrode generates a photocurrent wave (ca. 100 nA cm(-2)) in response to visible light irradiation.     

Proton-sensitive fluorescent organogels

A 1,10-phenanthroline-appended cholesterol-based gelator (1) and its nongelling reference compound (2) were synthesized. Among 19 solvents tested herein, gelator 1 could gelate 11 solvents including alcohols, dipolar aprotic solvents, organic acids and a base (triethylamine), indicating that 1 acts as a versatile gelator. The TEM observation gave a visual image showing that fibrillar aggregates are entangled in the three-dimensional network structure. In the fluorescence measurements, most gels afforded an emission maximum at 394 nm (purple emission), whereas only the acetic acid gel afforded an emission maximum at 522 nm (yellow emission). Thus, the influence of protonation of the 1,10-phenanthroline nitrogens (by trifluoroacetic acid) on the fluorescence properties in the gel phase was investigated in detail. The results have established that the fluorescence intensity of 1 x H+ becomes particularly strong in the gel phase, presumably because of the energy transfer from neutral 1* to protonated 1 x H+ and the restriction of the 1 x H+ molecular motion. The finding suggests the possibility that the gel system would be useful not only as a new proton-sensitive fluorescence system but also as a new medium for designing efficient energy transfer systems.     

First successful molecular design of an artificial Lewis oligosaccharide binding system utilizing positive homotropic allosterism

We have designed phenylboronic acid group appended Ce(IV) bis(porphyrinate) double decker 1 and meso-meso linked porphyrin 2, useful for the allosteric binding of biologically important saccharides, Lewis oligosaccharides. Compound 1 binds Lewis oligosaccharides in aqueous media because of the boronic acid-diol interaction, but the complexation event can occur only above the critical concentrations because of the sigmoidal [oligosaccharide] versus [complex] isotherm. Compound 1 has a sufficiently high affinity with Lewis oligosaccharides (K = 10(5)-10(6) M(-2)) with Hill coefficients n of 1.8-2.0, and Lewis(X) series and Lewis(a) series give opposite, symmetrical CD spectra. This is the first example of efficient binding of Lewis oligosaccharides to the artificial receptor, which has become possible by positive homotropic allosterism.     

Robustness to head misalignment of virtual sound imaging systems

When binaural sound signals are presented with two loudspeakers, the listener's ears are required to be in the relatively small region which is under control of the system. Misalignment of the head results in inaccurate synthesis of the binaural signals. Consequently, directional information associated with the acoustic signals is inaccurately reproduced. When the two loudspeakers are placed close together, the spatial rate of change of the generated sound field is much smaller than that generated by two loudspeakers spaced apart. Therefore, the performance of such a system is expected to be more robust to misalignment of the listener's head. Robustness of performance is investigated here with respect to head displacement in three translational and three rotational directions. A comparison is given between systems consisting of two loudspeakers either placed close together or spaced apart. The extent of effective control with head displacement and the resulting deterioration in directional information is investigated in the temporal and spectral domain by analyzing synthesized binaural signals. Subjective localization experiments are performed for cases in which notable differences in performance are expected from the previous analysis. It is shown that the system comprising two loudspeakers that are close together is very robust to misalignment of the listener's head.     

Universal torsion-induced interaction from large extra dimensions

We consider the Kaluza-Klein (KK) scenario in which only gravity exists in the bulk. Without the assumption of symmetric connection, the presence of brane fermions induces torsion. The result is a universal axial contact interaction that dominates those induced by KK gravitons. This enhancement arises from a large spin density on the brane. Using a global fit to Z-pole observables, we find the 3sigma bound on the scale of quantum gravity to be 28 TeV for n = 2. If Dirac or light sterile neutrinos are present, the data from SN1987A increase the bound to sqrt[n] M(S)>/=210 TeV.     

Radical and void formation in ultradrawn polyoxymethylene

In the production of ultrahigh-modulus (45–60 GPa) polyoxymethylene (POM) by microwave heating drawing, ultradrawing to draw ratios over 20 causes formation of numerous voids and radicals. The volume fraction of the internal voids is proportional to the drawing-induced radical concentration. On the basis of the idea that the rupture of taut tie-molecules (TTM) is responsible for void and radical formation, the relationship between the fraction of tiemolecules that are taut and the fraction that are ruptured is discussed by assuming both a Takayanagi structure model and the normal distribution of the tie-molecule lengths. The results indicate that longer tie-molecules are successively converted to TTM's followed by ruptures of shorter TTM's in the ultradrawing process; a small variance in the tie-molecule length distribution is effective for increasing TTM's without void formation. The maximum value of the volume fraction of taut tie-molecules for highly oriented POM tubes is estimated to be about 0.5.