Redox behavior of ferrocene-containing rotaxane: transposition of the rotaxane wheel by redox reaction of a ferrocene moiety tethered at the end of the axle

A rotaxane with a ferrocene moiety at the axle terminus was prepared. The redox potential of the ferrocene moiety decreased by ca. 80 mV when the rotaxane had a crown ether wheel capable of moving on the axle. Thus, the stabilization of the oxidized state of the ferrocene moiety is assumed to accompany the transposition of the wheel component on the axle toward the ferrocene moiety. [reaction--see text]     

Time-resolved study of intramolecular charge transfer fluorescence in 1,2,3,4-tetrachloro-11H-isoindolo-[2, 1-a]-benzimidazol-11-one

Fluorescent properties of 1,2,3,4-tetrachloro-11H-isoindolo-[2,1-a]-benzimidazol-11-one (TCIB) in various organic solutions are described. Detailed investigation of the fluorescence from the solutions revealed that it was ascribable to the electronic transition from the lowest singlet excited state of an isolated molecule to its ground state, though the fluorescence spectrum was broad and structureless and the Stokes’ shift was about 1 eV. The absorption peak of TCIB was relatively insensitive to change in solvent polarity, whereas its fluorescence peak shifted to the red with an increase in the polarity. This finding suggests that the dipole moment of the molecule in the ground state is almost zero, and that the excited state has a non-zero dipole moment, which coincides with the predicted semiempirical molecular orbital calculation. Fluorescence quantum efficiency decreased with increase of solvent polarity. The efficiency was reduced by a factor of 39 in going from n-hexane solution to acetonitrile solution. The radiative rate constant also decreased with increase of solvent polarity. However, its reduction was very moderate; the reduction factor was only 2.5 for acetonitrile solution as compared with n-hexane solution. This finding indicates that the emitting state of the title compound is influenced by a solvent-dependent non-radiative mechanism, for which solvent-sensitive intersystem-crossing deactivation is tentatively proposed.     

π-Face-selective hetero Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide. An excellent trapping reagent for thioaldehydes and thioketones

Hetero Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide (1) with thioaldehydes and thioketones take place exclusively, except the reaction with thiobenzophenone, at the syn-π-face of 1 with respect to the SO bond. The π-face selectivity was explained in terms of the extent of conformational changes of 1 that are brought about in the process to the transition states.     

A new ent-clerodane diterpene from the aerial parts of Baccharis gaudichaudiana

A new ent-clerodane diterpene, named bacchariol (1) was isolated from the aerial parts of Baccharis gaudichaudiana DC. (Compositae), together with known ent-clerodane diterpenes (2, 3), eight known flavonoids (4-11) and 3, 5-dicaffeoylquinic acid (12). Their structures were determined by spectroscopic analyses. Flavonoids (7, 8, 11) and 12 showed moderate scavenging activities toward 1, 1-diphenyl-2-picrylhydrazyl (DPPH) radicals.     

High-speed separation system of randomly suspended single living cells by laser trap and dielectrophoresis

We developed a new system for random separation of a single microorganism, such as a living cell and a microbe, in the microfluidic device under the microscope by integrating the laser-trapping force and dielectrophoretic (DEP) force. An arbitrarily selected single microbe could be isolated in a microchannel, despite the presence of a large number of microbes in solution. Once the target microbe is trapped at the focal point of the laser, we can easily realize exclusion of excess microbes around the target by controlling the electric field, while keeping the target trapped by the laser at the focal point. To realize an efficient separation system, we proposed a new separation cell and produced it by microfabrication. Flow speed in the microchannel is adjusted and balanced to realize high-speed and high-purity extraction of the target. Some preliminary experiments are conducted to show the effectiveness. The target is trapped by the laser, transported, and is taken out from the extraction port. Total separation time is less than 20 s. Our method is extremely useful in the pure cultivation of the cell and will be a promising method for biologists in screening useful microbes.     

An Adaptive Algorithm for Vector Partitioning

The vector partition problem concerns the partitioning of a set A of n vectors in d-space into p parts so as to maximize an objective function c which is convex on the sum of vectors in each part. Here all parameters d, p, n are considered variables. In this paper, we study the adjacency of vertices in the associated partition polytopes. Using our adjacency characterization for these polytopes, we are able to develop an adaptive algorithm for the vector partition problem that runs in time O(q(L)v) and in space O(L), where q is a polynomial function, L is the input size and v is the number of vertices of the associated partition polytope. It is based on an output-sensitive algorithm for enumerating all vertices of the partition polytope. Our adjacency characterization also implies a polynomial upper bound on the combinatorial diameter of partition polytopes. We also establish a partition polytope analogue of the lower bound theorem, indicating that the output-sensitive enumeration algorithm can be far superior to previously known algorithms that run in time polynomial in the size of the worst-case output.     

Chirped-pulse amplification of ultraviolet femtosecond pulses by use of Ce(3+):LiCaAlF(6) as a broadband, solid-state gain medium

Chirped-pulse amplification in the ultraviolet region is demonstrated by use of a broadband Ce(3+): LiCaAlF(6) laser medium. A modified bow-tie-style four-pass amplifier pumped by 100-mJ, 266-nm pulses from a Q -switched Nd:YAG laser has a gain factor of 370 and delivers 6-mJ, 290-nm pulses. After dispersion compensation, the output pulses can be compressed to 115 fs.     

Room-temperature Tm, Ho:LuLiF(4) laser with a novel quasi-end-pumping technique

A novel diode-pumped, efficient, quasi-end-pumping scheme that uses two lens ducts to achieve homogeneous pumping in a gain medium was proposed and evaluated. With this technique, room-temperature laser action at a pulse repetition frequency up to 20 Hz was demonstrated in 5%Tm, 0.5%Ho:LuLiF(4), which we grew by the Czochralski method. At 10 Hz a long-pulse laser output energy in excess of 24 mJ and a slope efficiency with respect to the incident pump energy of 10.7% were obtained.     

A new synthesis of enantiomerically pure α- and β-amino acid derivatives using aziridinyl anions

Optically active sulfinylaziridines having a 4-methoxyphenyl group on their nitrogen atom were synthesized from optically active 1-chloroalkyl p-tolyl sulfoxide and an imine derived from benzaldehyde and p-anisidine stereoselectively in good overall yields. The sulfinylaziridines were treated with ethylmagnesium bromide or tert-butyllithium to afford aziridinylmagnesiums or aziridinyllithiums, respectively, in quantitative yields. Cross-coupling of the aziridinylmagnesiums with iodoalkanes in the presence of Cu(I) iodide gave tri-substituted aziridines in high yields from which enantiomerically pure β,β-disubstituted β-amino acid derivatives were synthesized. A β-amino acid derivative having deuterium at the stereogenic center was also realized by this method. On the other hand, from the aziridinyllithium, enantiomerically pure quaternary phenylalanine and quaternary aspartic acid derivatives were synthesized.