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.     

First total synthesis of a new sesquiterpenoid natural product, (±)-3-(2,4-dihydroxybenzoyl)-4,5-dimethyl-5-(4,8-dimethyl-3(E),7(E)-nonadien-1-yl)tetrahydro-2-furanone

An efficient and stereodefined process is described for the first preparation of a new prenyl-benzoylfuranone type sesquiterpenoid, (±)-3-(2,4-dihydroxybenzoyl)-4,5-dimethyl-5-(4,8-dimethyl-3(E),7(E)-nonadien-1-yl)tetrahydro-2-furanone. The synthetic strategy is based on nucleophilic addition of organometallic reagents to the functionalized ketoamides elaborated from dihydroxyacetone dimer for the stereoselective construction of the key quaternary carbon center in the target compound.     

Band gap engineering of CdTe nanocrystals through chemical surface modification

We demonstrate band gap control of CdTe nanocrystals by selective surface modification using alkanethiol molecules. Both absorption and emission wavelengths can be tuned simply by mixing a dispersion of the nanocrystals with alkanethiol at room temperature, resulting in blue shifts in the optical spectra during reaction. The degree of blue shift depends on both the concentration of alkanethiols and the reaction time, thereby providing kinetic control over the emission peak wavelength of the nanocrystals in mild conditions. The observed spectral changes are suggested to be caused by a decrease in the size of the CdTe core through formation of CdTe1-x(SC10)x shells because of specific exchange of Te with alkanethiolates. The results reported herein provide a new band gap engineering scheme for semiconductor nanocrystals and offer opportunities for the design of ligand-stabilized semiconductor nanocrystals with tunable composition and optical properties.     

H2 generation during dry grinding of kaolinite

H2 generation during mechanochemical treatment of kaolinite by dry grinding was examined by X-ray diffraction analysis, Fourier transform infrared spectroscopy, and BET surface area measurement. The H2 concentration in the mill pot, measured by gas chromatography, increased with grinding time up to a maximum concentration of 156 ppm (0.35 micromol) after 600 min. This H2 generation is considered to occur as a result of three processes: (1) structural destruction characterized by the delamination and loss of hydroxyl groups as a result of dry grinding, (2) transformation of liberated hydroxyls into water molecules by mechanochemical effects such as prototropy, and (3) H2 generation through reaction between surface water molecules and mechanoradicals created by the rupture of Si-O or Al-O-Si bonds. Although the surface area plateaued after 240 min grinding, the H2 concentration continued to increase, indicating that surface mechanoradicals are created during this later grinding stage. Thus, H2 generation can be used as an indicator of mechanoradical formation during mechanochemical treatment.     

Negative azeotropy in mixed adsorption of hexanol and dodecylammonium chloride at water/air interface

Miscibility of hexanol and dodecylammonium chloride (DAC) in adsorbed films and micelles was investigated by evaluating the compositions of the adsorbed films and micelles from surface tension measurements. Judging from the phase diagram of adsorption, negative azeotropy of adsorption was observed for the mixed adsorption of hexanol and DAC at water/air interfaces. The nonideal mixing in the adsorbed film was clarified using excess functions of adsorption. Interaction between hexanol and DAC in the adsorbed film was compared with that between other alkanols and surfactants. It was found that the range of azeotropes is narrower for the hexanol-DAC mixture than for the heptanol-octylsulfinylethanol mixture, because interaction between different species in an adsorbed film is weaker in the former than in the latter.     

SmI2-promoted tandem desulfurization and reductive coupling reactions of aromatic lactams with carbonyl compounds

Treatment of sulfur-substituted aromatic lactams with carbonyl compounds in the presence of samarium(II) diiodide was found to undergo novel tandem desulfurization and reductive coupling reactions to generate -hydroxyalkylated lactams in high yield. Stereochemistry of the coupling products was researched and the results that decreasing the steric bulkiness of the N-substituents as well as raising the reaction temperature leads to an increase of the erythro-selectivity were observed. The mechanistic origins of this stereoselectivity are also briefly documented.     

Quantitative analysis of organic additive content in a polymer by ToF-SIMS with PCA

Quantitative analysis of organic materials by ToF-SIMS is intrinsically difficult because of their tendency to decompose under ion irradiation. In this study, we applied principal component analysis (PCA) as a means of compensation for the spectral degradation caused by this decomposition and thus improve the accuracy of the quantitative analysis, using as models two organic additives of quite different composition and vulnerability to decomposition under ion irradiation, in polystyrene. This enables the extraction of a principal component related to their content that is independent of the decomposition. The effectiveness of this approach in quantitative analysis of organic additives content in polymers without loss in accuracy due to spectral degradation will be discussed.     

Theoretical study on quantum dynamics of bose system interacting with photon field

We investigate the quantum dynamics of two‐boson and two‐level systems interacting with a one‐mode photon field. The time evolution of the population for each state is calculated in terms of the Jaynes–Cummings model. We find the collapses and revivals of the order parameter for the Bose–Einstein condensation. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 401–408, 2001     

Inverted micelle formation of cell-penetrating peptide studied by coarse-grained simulation: importance of attractive force between cell-penetrating peptides and lipid head group

Arginine-rich peptide and Antennapedia are cell-penetrating peptides (CPPs) which have the ability to permeate plasma membrane. Deformation of the plasma membrane with CPPs is the key to understand permeation mechanism. We investigate the dynamics of CPP and the lipid bilayer membrane by coarse-grained simulation. We found that the peptide makes inverted micelle in the lipid bilayer membrane, when the attractive potential between the peptide and lipid heads is strong. The inverted micelle is formed to minimize potential energy of the peptide. For vesicle membrane, the peptide moves from the outer vesicle to the inner vesicle through the membrane. The translocation of the peptide suggests inverted micelle model as a possible mechanism of CPPs.