A new general route to thiophenophanes: synthesis and properties of [n](2,5)thiophenophane-1,n-diones

A series of [n](2,5)thiophenophane-1,n-diones (5) (n = 9, 10, 12, 14, 16, and 20) were synthesized in a simple four-step route starting from the appropriate 1,omega-oligomethylenedicarboxylic acids. The bis(halomethylketones) (6), which were obtained by successive treatment of the diacids with SOCl2, diazomethane, and HBr or HCl, were cyclized by Na2S under high dilution conditions. The obtained monomeric cyclic diketosulfides (4) were condensed with glyoxal in MeOH by slowly adding dilute NaOMe affording 5. The thiophene-2,5-dicarbonyl moiety of 5 (n = 9) is significantly deformed as shown by X-ray crystallography, and the effect of the strain is reflected in the C=O stretching frequencies and the pi-pi* and the n-pi* absorptions.     

A novel quinoline alkaloid possessing a 7-benzyl group from the centipede, Scolopendra subspinipes.

The novel quinoline alkaloid scolopendrine was isolated from the centipede, Scolopendra subspinipes mutilans L. Koch. The structure was determined to be 2-hydroxy-7-[(4-hydroxy-3-methoxyphenyl)methyl]-3-methoxy-8-quinolyl sulfate on the basis of high-resolution electron-spray ionization mass spectroscopy and two-dimensional NMR spectral data. Unlike quinoline alkaloids so far reported, scolopendrine is unique in having a 7-benzyl moiety in the quinoline ring.     

Wake properties of a single gas bubble in three-dimensional liquid-solid fluidized bed

Experiments were performed to investigate the wake properties of a single gas bubble in a three-dimensional liquid-solid fluidized bed via a video camera moving at the same speed as the bubble. The solids holdup in the fluidized bed varied up to around 10%. The bubble size varied from 5 to 20 mm with corresponding bubble Reynolds numbers ranging from 1000 to 6500. The bubble was observed to have two types of wake configurations depending on the bubble size: the asymmetric/helical vortex wake for small bubbles and the symmetric wake for large bubbles. The bubble shape and relative rise velocity in the fluidized bed can be well-represented by correlations developed for single bubbles in liquid media, although the bubble shape in liquid-solid media is slightly more flattened compared to that in liquid media. The bubble rocking frequency was found to be independent of particle properties and to correspond in magnitude to the vortex shedding frequency in a two-dimensional liquid-solid fluidized bed. The average primary wake size in three dimensions is comparable to that in two dimensions.     

Molecular recognition in a supramolecular hydrogel to afford a semi-wet sensor chip

This communication describes a new molecular recognition chip using a semi-wet microenvironment provided by a self-assembled hydrogel. On the basis of the evidence that the molecular recognition capability of artificial chemosensors are practically retained even in the hydrogel compared to those in aqueous solution, we miniaturized the functionalized hydrogel to produce an unprecedented molecular recognition chip. We believe that the present noncovalent immobilization method is generally applicable to many chemosensors, which leads to a unique semi-wet sensor chip suitable to convenient and high-throughput assay to plural analytes.     

Synthesis of N,N,N′,N′-tetrasubstituted 1,3-bis(4-aminophenyl)azulenes and their application to a hole-injecting material in organic electroluminescent devices

After a preliminary search of the reaction conditions for the Suzuki-Miyaura cross-coupling of haloazulenes with arylboronic acids, the title compounds were synthesized either by the direct coupling reaction between 1,3-dihaloazulene and the corresponding N,N-disubstituted 4-aminophenylboronic acids or by a two-step sequence involving the cross-coupling with 4-bromophenylboronic acid and subsequent Pd-catalyzed amination. Application of the title diamines to a hole-injecting material in organic electroluminescent devices was carried out to provide their prominent characteristics as a novel durable, non-cyanine and non-polyamine substance without color fade. The diamine derivatives, extended by an ethynyl unit between the azulenyl core and the 4-aminophenyl moiety, were also synthesized and found, unfortunately, unsuitable for vacuum deposition in preparing a multilayer composite.