Mass spectrometric analysis of low molecular mass polyesters by laser desorption/ionization on porous silicon

A low molecular mass polyester was analyzed by desorption/ionization on porous silicon (DIOS) mass spectrometry. The results were compared with those of matrix-assisted laser desorption ionization (MALDI) mass spectrometry using matrixes of alpha-cyano-4-hydroxycinnamic acid (CHCA) and 10,15,20-tetrakis(pentafluorophenyl)porphyrin (F20TPP). The CHCA matrix was not suitable for characterization of low molecular mass components of the polyester because the matrix-related ions interfered with the component ions. On the other hand, the F20TPP matrix showed no interference because no matrix-related ions appeared below m/z 822. However, the solvent selection for determining optimal conditions of sample preparation was limited, because F20TPP does not dissolve readily in any of the available organic solvents. In the DIOS spectra, the polymer ions were observed at high sensitivity without a contaminating ion. No matrix is needed for DIOS spectra of low molecular mass polyesters, facilitating sample preparation and selectivity of a precursor ion in post-source decay measurements.     

Reaction of indium ate complexes with allylic compounds. Controlling SN2/SN2′ selectivity by solvents

Vinyl and methylindium ate complexes (indates) were prepared and both the tendency of immigration and regioselectivity toward cinnamyl bromide were investigated. The vinyl group was more preferably transferred than the Me group, giving a regioisomeric mixture of S_N2 and S_N2′ products. The ratio of S_N2/S_N2′ selectivity can be controlled by solvents; in the presence of polar solvents, such as N-butylpyrrolidone (NBP) and THF, the S_N2′ product was mainly obtained, whereas the S_N2 product was selectively prepared in solutions containing hexane. The vinylindium compound, generated by the reaction of allylic-type diindium reagents with imine, was also converted to the corresponding vinyl indate, which was allowed to react with allyl chloride to give a three-component coupling product.     

On the correlation between NQR frequency and bond length in I3−

A linear correlation between the NQR frequency of the terminal iodine atom and the corresponding I-I bond length in I₃^? was found in several compounds containing triiodide anions. A simple extended Huckel MO calculation suggested that such a correlation can be used to check the validity of wavefunctions of iodine.     

Radiocarbon dating of an ancient Japanese document “Minamoto no Yoritomo Sodehan Migyosho” by accelerator mass spectrometry

We measured radiocarbon age of an ancient document “Minamoto no Yoritomo Sodehan Migyosho”. The content tells that it was issued in 1189 by “Minamoto no Yoritomo” known as the virtually first shogun in Japan to grant “Matsugi” family the privilege of controlling craftsmen of foundry industry. Paleographical views, however, suggested that it can be a counterfeit. The radiocarbon dating clarified that the document was written not in the 12th but after the 16th century.