Short synthesis of alkyl-substituted acenes using carbonyl-directed C-h and C-o functionalization

A convenient method for the synthesis of tetraalkylanthracenes and -pentacenes by means of ruthenium-catalyzed regioselective C-H alkylation of the corresponding acenequinones was developed. Dialkyldiarylpentacene was also synthesized using chemoselective tandem C-H alkylation/C-O arylation of dimethoxypentacenequinone. It was suggested that a tetraalkylpentacene is stable under air in the dark and possesses an appropriate HOMO level as active material for p-type organic field-effect transistors (OFETs).     

Identification of oligosaccharides from histopathological sections by MALDI imaging mass spectrometry

Direct tissue analysis using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) provides the means for in situ molecular analysis of a wide variety of biomolecules. This technology—known as imaging mass spectrometry (IMS)—allows the measurement of biomolecules in their native biological environments without the need for target-specific reagents such as antibodies. In this study, we applied the IMS technique to formalin-fixed paraffin-embedded samples to identify a substance(s) responsible for the intestinal obstruction caused by an unidentified foreign body. In advance of IMS analysis, some pretreatments were applied. After the deparaffinization of sections, samples were subjected to enzyme digestion. The sections co-crystallized with matrix were desorbed and ionized by a laser pulse with scanning. A combination of α-amylase digestion and the 2,5-dihydroxybenzoic acid matrix gave the best mass spectrum. With the IMS Convolution software which we developed, we could automatically extract meaningful signals from the IMS datasets. The representative peak values were m/z 1,013, 1,175, 1,337, 1,499, 1,661, 1,823, and 1,985. Thus, it was revealed that the material was polymer with a 162-Da unit size, calculated from the even intervals. In comparison with the mass spectra of the histopathological specimen and authentic materials, the main component coincided with amylopectin rather than amylose. Tandem MS analysis proved that the main components were oligosaccharides. Finally, we confirmed the identification of amylopectin by staining with periodic acid-Schiff and iodine. These results for the first time show the advantages of MALDI-IMS in combination with enzyme digestion for the direct analysis of oligosaccharides as a major component of histopathological samples.     

Random partitioning over a sparse contingency table

The present article investigates a class of random partitioning distributions of a positive integer. This class is called the limiting conditional compound poisson (LCCP) distribution and characterized by the law of small numbers. Accordingly the LCCP distribution explains the limiting behavior of counts on a sparse contingency table by the frequencies of frequencies. The LCCP distribution is constructed via some combinations of conditioning and limiting, and this view reveals that the LCCP distribution is a subclass of several known classes that depend on a Bell polynomial. It follows that the limiting behavior of a Bell polynomial provides new asymptotics for a sparse contingency table. Also the Neyman Type A distribution and the Thomas distribution are revisited as the basis of the sparsity.     

Total synthesis of antimalarial diterpenoid (+)-kalihinol A

Total synthesis of antimalarial diterpenoid (+)-kalihinol A, isolated from marine sponge Acanthella sp., is achieved. This total synthesis involves regioselective alkylation of an epoxide, construction of a tetrahydropyran ring by iodo-etherification, construction of a cis-decalin ring by intramolecular Diels-Alder reaction, isomerization of cis-decalin to trans-decalin, and subsequent functionalization of the trans-decalin ring.     

Copper-catalyzed coupling reaction of unactivated secondary alkyl iodides with alkyl Grignard reagents in the presence of 1,3-butadiene as an effective additive

Cu-catalyzed cross-coupling of unactivated secondary alkyl iodides with alkyl Grignard reagents in the presence of 1,3-butadiene as a ligand precursor was developed. The use of 1,3-butadiene resulted in improved yields of alkyl-alkyl products with improved selectivities.     

Influence of water on molecular forms of rhodamine B in dip-coated thin films

Dip-coated thin films including rhodamine B have been prepared using the sol-gel reaction of tetraethyl orthosilicate under relative humidity of 30% and 60%. They have been aged under relative humidity of 20%, 60%, and 95% for 5 days. According to the absorption spectra, just after the preparation of the films and under higher humidity, a larger amount of the dimers (H-and J-types) were formed in the films. Five days after the preparation of the films and aged under higher humidity, the H-dimer increased. On the other hand, the J-dimer increased, regardless of humidity under which the films were aged.     

Reactions of 2-Pyridyl Substituted Phosphine Oxides and Phosphonium Salts with Organometallic Reagents and in Aqueous Media

Phosphine oxides bearing two or three 2-pyridyl groups react with organometallic reagents affording 2,2′-bipyridyl, 2-substituted pyridines and pyridine in good yields. Phosphonium salts and phosphine oxides, bearing at least two 2-pyridyl or substituted 2-pyridyl groups also give the corresponding 2,2′-bipyridyls and pyridines upon treatment with acid or neutral solvents such as water and alcohols in substantial yields. The 2,2′-bipyridyls are considered to be formed by ligand coupling within the pentacoordinated phosphorus intermediate formed incipiently during the reaction.     

Surface viscous flattening kinetics of soda-lime silicate glass by sinusoidal profile decay method

The kinetics of the flattening of surface corrugations of float glasses were investigated in dry nitrogen at 610 to 670°C. The amplitude of the sinusoidal surface profile decayed exponentially with time while its wavelength remained constant. The dependence of decay rate on wavelength indicated that the process is controlled by the viscous flow. From the obtained rate constant the viscosity was calculated using the surface energy value determined independently by the zero-creep method. The viscosity thus obtained reflects the mass transport property in the vicinity of the glass surface. It was several times larger than that determined by the fibre elongation or intrusion method which should reflect the bulk properties. No difference in the decay rate was observed on both the surfaces of float glass of which only one side had been exposed to molten tin during the glass manufacturing process.