Time-resolved fluorescence spectroscopic and scanning near-field optical microscopic studies of rhodamine dye adsorbed in cationic Langmuir-Blodgett films

The fluorescence lifetimes decays and picosecond time-resolved fluorescence spectra were measured to investigate the dynamics of the excited state of sulforhodamine B (SRB) molecules adsorbed in the mono- and multilayered Langmuir-Blodgett (LB) films of octadecylamine. Steady-state and time-resolved fluorescence spectroscopy reveals that the fluorescence lifetimes and contents of the monomer and dimers in the molecular organizates depend upon the concentration of the dye in the solution and the adsorption process. SRB dye molecules adsorbed in LB films have been imaged with scanning near-field optical microscopy (SNOM). This information is exploited to map the distribution with molecular spatial resolution. SNOM provide the visual evidence of the monomers and dimers of SRB in cationic LB films.     

Synthesis and cation-binding properties of poly-and bis(thiacrown ether)s

Poly- and bis(thiacrown ether) derivatives in which some oxygen atoms of benzocrown ether moiety are replaced by sulfur atoms have been synthesized. Their cation-binding abilities were investigated by using the solvent extraction method. The poly- and bis(benzothiacrown ether)s showed great affinity for silver ion, being more excellent in the affinity than the corresponding monocyclic analogs. They, however, possess very poor cation-binding ability for alkali and alkaline-earth metal ions. The poly- and bis(thiacrown ether)s also bind mercuric ions effectively, whereas the corresponding monomeric analogs do not at all.     

A quantitative analysis of the through-space and the through-bond interactions between lone-pairs in azines: pyridazine,pyrimidine and pyrazine

The INDO calculations were performed on the three azines: pyridazine, pyrimidine, and pyrazine. The cannonical molecular orbitais obtained by these calculations were then transformed into the localized molecular orbitals. With the use of the localized molecular orbitals, the variation in the lone-pair orbital energies of these molecules were pursued in the light of the through-space and/or the through-bond interactions between the specified localized molecular orbitals in a molecule selectively. The interactions were expressed by the summation of several terms: through-space, through-bond, through-virtuals and coupling terms.     

Spin-lattice relaxation time as a useful indicator for the 13CNMR assignment of terminal cis- and trans-methyls in 2-methyl-1-propenyl moiety

T₁ gives a clue to assign cis- and trans-methyl carbons in 2-methyl-1-propenyl moiety.     

Alternating copolymers consisting of arylalkyl methacrylates. I. Fluorescence properties of poly(arylalkyl methacrylate-alt-styrene) in organic solution

Alternating and random copolymers of 9-phenanthrylmethyl methacrylate or 2-(9-carbazolyl)ethyl methacrylate with styrene were synthesized and their fluorescence properties were examined. There was no noticeable difference in the spectral features of the alternating and random copolymers in tetrahydrofuran (THF), demonstrating that this type of polymers have no quenching sites in the polymer chains. The fluorescence quenching studies indicated that the alternating copolymers permitted singlet-state energy migration as efficiently as the corresponding random copolymers but less efficiently than the random copolymers with higher chromophore contents. These results strongly suggest that to be chromophores close to each other is most important for facilitation of an intramolecular energy migration. © 1995 John Wiley & Sons, Inc.     

Oxovanadium(V)-catalyzed enantioselective Meerwein-Ponndorf-Verley cyanation of aldehydes using acetone cyanohydrin

Oxovanadium(V)(salen) complex 4 was found to catalyze Meerwein-Ponndorf-Verley cyanation of aliphatic aldehydes with good to high enantioselectivity. This cyanation showed a positive nonlinear effect.     

Gelation in free-radical terpolymerization of poly(allyl methacrylate) crosslinked polymer nanosphere with allyl benzoate and vinyl benzoate

Microgel-like poly(allyl methacrylate) (PAMA nanosphere) was prepared by the emulsion polymerization of AMA as the reactive crosslinked polymer nanosphere with abundant pendant allyl groups. The terpolymerization of PAMA nanosphere with allyl benzoate (ABz) and vinyl benzoate (VBz) was conducted in bulk using benzoyl peroxide as initiator at 80 °C. The gelation depended on the feed ABz/VBz molar ratio since the molecular weights of resulting poly(ABz-co-VBz)s that act as the bridges increased with an increase in the mole fraction of VBz in the feed monomer. Beyond the gel point, the sol was rapidly incorporated into the gel and the increasing tendency of the gel fraction became steeper from 70 to 95 mol% of VBz as a reflection of increased chain length of bridge between PAMA nanospheres. Moreover, the swelling ratio became lower with increasing the mole percentage of VBz in the feed monomer. These results would support the preferential incorporation of PAMA nanosphere into the gel and the longer bridge can capture more nanospheres to give a much shrunken gel.     

Lead-selective poly(vinyl chloride) membrane electrodes based on acyclic dibenzopolyether diamides

Lipophilic acyclic dibenzopolyether diamides, 12 kinds, have been designed to prepare solvent polymeric membrane ion-selective electrodes (ISEs) for Pb(2+). The ionophores include 1,5-bis[2-(N,N-dialkylcarbamoylmethoxy)phenoxy]-3-oxapentanes1-4, 1,5-bis[2-(N,N-dialkylcarbamoylpentadecyloxy)phenoxy]-3-oxapentanes 5-8, and 1,2-bis[2-(2'-N,N-dialkylcarbamoylpentadecyloxy)phenoxy]ethanes 9-12. Linear response concentration range of the ISE based on 9 is 3 x 10(-2) - 1 x 10(-6) M of Pb(2+) (average slope = 28.5 mV decade(-1)). Potentiometric selectivities of the ISEs based on 1-12 for Pb(2+) over other heavy metal cations, alkali metal cations, and alkaline earth metal cations have been assessed. These ISEs exhibit remarkably high selectivities for Pb(2+) relative to heavy metal cations, such as Cu(2+), Fe(2+), and Ni(2+), the selectivity coefficients (K(Pot)(Pb,Cu)) being 5 x 10(-5) - 6 x 10(-5) for 1-4 and ca. 6 x 10(-4) for 9. For the Pb(2+) selectivities over alkali metal cations, such as Na(+) and K(+), 9 which has an ethylene glycol spacer and a N,N-diethyl group is superior to other dibenzopolyether diamide ionophores 1-8 and 10-12.     

Asymmetric skeletal rearrangement of symmetrically alpha,alpha-disubstituted alpha-amino aldehydes: a new entry to optically active alpha-hydroxy ketones

A unique asymmetric skeletal rearrangement of symmetrically alpha,alpha-disubstituted alpha-amino aldehydes has been accomplished for the first time using a chiral organoaluminum Lewis acid 1. For instance, treatment of (S)-2,2'-bis(trifluoromethanesulfonylamino)-1,1'-binaphthyl with Me3Al (1.0 equiv) in toluene at room temperature for 15 min and at 110 degrees C for an additional 15 min produced (S)-1, and a subsequent reaction with alpha -amino aldehyde 2a (R = CH2Ph) at -78 degrees C for 4 h and at -40 degrees C for 12 h resulted in the smooth rearrangement to the zwitterionic iminium intermediate A, which furnished the alpha-hydroxy ketone 3a (R = CH2Ph) in 93% isolated yield with 95% ee (S) after acidic hydrolysis. This result, together with other representative examples, clearly demonstrates the effectiveness of the present method for the hitherto difficult asymmetric synthesis of acyloins. Furthermore, we found that the treatment of the in situ generated A with DIBAH afforded the corresponding anti amino alcohol exclusively without loss of enantiomeric excess. Our approach casts light on the previously unexplored yet potential utility of alpha-amino aldehydes as synthetic building blocks and also provides a new entry to optically active alpha-hydroxy ketones and 1,2-amino alcohols.