Heterodimerization of dye-modified cyclodextrins with native cyclodextrins

The heterodimerization behavior of dye-modified beta-cyclodextrins (1-6) with native cyclodextrins (CDs) was investigated by means of absorption and induced circular dichroism spectroscopy in an aqueous solution. Three types of azo dye-modified beta-CDs (1-3) show different association behaviors, depending on the positional difference and the electronic character of substituent connected to the CD unit in the dye moiety. p-Methyl red-modified beta-CD (1), which has a 4-(dimethylamino)azobenzene moiety connected to the CD unit at the 4' position by an amido linkage, forms an intramolecular self-complex, inserting the dye moiety in its beta-CD cavity. It also associates with the native alpha-CD by inserting the moiety of 1 into the alpha-CD cavity. The association constants for such heterodimerization are 198 M(-1) at pH 1.00 and 305 M(-1) at pH 6.59, which are larger than the association constant of 1 for beta-CD (43 M(-1) at pH 1.00). Methyl red-modified 2, which has the same dye moiety as that for 1 although its substituent position is different from that of 1, does not associate even with alpha-CD due to the stable self-intramolecular complex, in which the dye moiety is deeply included in its own cavity of beta-CD. Alizarin yellow-modified CD (3), which has an azo dye moiety different from that of 1 and 2, caused a slight spectral variation upon addition of alpha-CD, suggesting that the interaction between 3 and alpha-CD is weak. On the other hand, phenolphthalein-modified beta-CD (4), which forms an intermolecular association complex in its higher concentrations, binds with beta-CD with an association constant of 787 M(-1) at pH 10.80, where 4 exists as the dianion monomer in the absence of beta-CD. p-Nitorophenol-modified beta-CDs (5 and 6), each having p-nitorophenol moieties with a different connecting part with an amido and amidophenyl group, respectively, associated with alpha-CD with association constants of 66 and 16 M(-1) for 5 and 6, respectively. The phenyl unit in the connecting part of 6 may prevent the smooth binding with alpha-CD. All these results suggest that the dye-modified CDs, in which the dye part is not tightly included in its CD cavity, associate with the native CD to form heterodimer composed of two different CD units by inserting the dye moiety into the native CD unit. The resulting heterodimers have a cavity that can bind another appending moiety of host molecules. On this basis, more ordered molecular arrays or the supramolecular hereropolymers can be constructed.     

Asymmetric synthesis of anti- and syn-beta-amino alcohols by reductive cross-coupling of transition metal-coordinated planar chiral arylaldehydes with aldimines

Samarium iodide-mediated cross-coupling of N-tosyl ferrocenylideneamine with planar chiral ferrocenecarboxaldehydes or benzaldehyde chromium complexes gave diastereoselectively the corresponding anti-beta-amino alcohol derivatives in good yields, while N-tosyl benzylideneamine produced syn-beta-amino alcohols by coupling with planar chiral arylaldehydes. Dynamic kinetic resolution of a configurationally equilibrated reactive species generated from achiral N-tosyl ferrocenilideneamine and benzylideneamine by reduction with samarium iodide was observed in the cross-coupling with planar chiral arylaldehydes giving both antipodes of beta-amino alcohols depending on the planar chirality. The obtained anti-beta-amino alcohol with the ferrocene ring was utilized as a chiral ligand for catalytic asymmetric reduction of acetophenone.     

Temperature dependence of photoluminescence spectra in n-type modulation-doped quantum dot arrays

Temperature dependence of photoluminescence (PL) spectra of an electrostatically prepared modulation-doped quantum dot array is investigated. We report a strong temperature dependence of the enhanced PL near the Fermi energy between 0.4 and 4.2 K under a negative bias condition, where an interconnected quantum dot array is formed. This strong temperature dependence suggests that the Fermi-surface-mediated many-body interaction between a photo-created hole and the electron-gas plays an important role in the observed enhanced PL near the Fermi energy.     

Two-electron and four-electron periodicity in single-wall carbon nanotube quantum dots

Single quantum dots have been fabricated in single-wall carbon nanotubes and electrical transport properties have been measured at low temperature. Two- and four-electron periodicities have been clearly observed in the same sample in different gate voltage ranges. The former is an even–odd effect which originates from the spin degeneracy, while the latter is related to the additional two-fold band degeneracy. The results are discussed with the energy scales associated with the dot, and the possibility for a single spin manipulation is suggested.     

Synthesis and characterization of double thermo‐responsive block copolymer consisting N‐isopropylacrylamide by atom transfer radical polymerization

In this thesis, we studied the convenient synthesis and characterizations of thermo‐responsive materials with double response. To achieve these, AB‐type diblock copolymers comprising of poly(N‐isopropylacrylamide) (NIPAAm) segment and poly(NIPAAm‐co‐(N‐(hydroxymethyl)acrylamide) (HMAAm)) one were designed. That was synthesized in one‐pot using an atom transfer radical polymerization (ATRP) technique. Poly(NIPAAm‐co‐HMAAm)s synthesized separately showed sensitive thermo‐response and the cloud point was completely tunable by the composition of HMAAm. As expected, the block copolymers exhibited double thermo‐responsive profiles in aqueous solution. The responsive behavior was discussed by precise trace by ¹H NMR and turbidity measurements. From these results, we could confirm almost independent dehydration of each segment. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6142–6150, 2008     

Visualization of the local ionic wind profile in a DC corona discharge field by laser-induced phosphorescence emission

Experimental visualization for ionic wind motion originated from DC corona discharges in a needle-plate electrode system has been investigated. A vapor-phase biacetyl tracer with laser-induced phosphorescence emission is used for optically characterizing the ionic wind profile. The ionic wind blows the excited biacetyl molecules away in continuing the visible phosphorescence emission for a long radiative lifetime. The captured image with elapsing time from the excitation presents the shifting location of radiative tracer along the ionic wind direction. The experimental results show the ionic wind profile enhanced in the electric field direction corresponding to the corona discharge progress. Especially, the ionic wind near an initiating point of corona discharges is focused as an advantage of this optical technique. The ionic wind velocity along the electrode axis can be obtained at the location close enough to the corona discharge initiation point, and the velocity at 0.5 mm from the discharge point is figured out as 9.3 to 19.2 m/s under the condition of the EHD Reynolds number of 0.95×10³ to 2.1×10³.     

Gate-voltage dependence of zero-bias anomalies in multiwall carbon nanotubes

Temperature dependence of zero-bias conductance of the vanadium (V)/multiwall carbon nanotube (MWNT)/V structure is studied. As temperature is reduced, the conductance decreases with a functional form consistent with a power law. For the first time, we find that the exponent depends significantly on gate voltage. This exponent dependence cannot be explained by Luttinger-liquid theory for ballistic MWNTs. We interpret the obtained results within the framework of the nonconventional Coulomb blockade theory for strongly disordered MWNTs.     

Dynamical quark effects on light quark masses

Light quark masses are calculated in lattice QCD with two degenerate flavors of dynamical quarks. The calculations are made with improved actions with lattice spacing a = 0.22-0.11 fm. In the continuum limit we find m(M&Smacr;)(ud)(2 GeV) = 3.44(+0.14)(-0.22) MeV using the pi and rho meson masses as physical input, and m(M&Smacr;)(s)(2 GeV) = 88(+4)(-6) MeV or 90(+5)(-11) MeV with the K or straight phi meson mass as additional input. The quoted errors represent statistical and systematic combined, the latter including those from continuum and chiral extrapolations, and from renormalization factors. Compared to quenched results, two flavors of dynamical quarks reduce quark masses by about 25%.