Phase-modulation fluorometer using a phase-modulated excitation light source

We propose a phase-modulation fluorometer (PMF) with a light-emitting diode (LED) or a laser diode (LD) used as an excitation light source (ELS) that is driven in the phase-modulation (PM) mode. The PM-ELS generates many frequency sidebands that spread in the vicinity of carrier frequency f _c with the interval of modulation frequency f _m depending on the maximum phase deviation Δφ. The scheme enables us to derive fluorescence lifetime values of a multicomponent sample at one time. We show a typical numerical simulation result for explaining the principle of operation. To demonstrate the effectiveness of the proposed PMF, we have measured fluorescence lifetimes of three kinds of inorganic fluorescent glasses and that of a mixture solution of 1 × 10^?6M rhodamine 6G and 1 × 10^?6 M coumarin 152 in ethanol with a volume ratio of 1: 1.     

Reactions of 2-phospholene 1-oxides with bromine in some media: Facile preparation of bromohydrin derivatives of 2-phospholenes

Reactions of 1-phenyl- and 1-methoxy-2-phospholene 1-oxides with bromine in aqueous organic solvents or in a protic medium, such as methanol, easily afforded the corresponding 2-bromo-3-hydroxy- or 2-bromo-3-methoxyphospholane 1-oxide derivatives. The reaction mechanism was postulated based on the stereochemistry of the products.     

Efficient Transformation of Polymer Main Chain Catalyzed by Macrocycle Metal Complexes via Pseudorotaxane Intermediate

Post-synthesis modification of polymers streamlines the synthesis of functionalized polymers, but is often incomplete due to the negative polymer effects. Developing efficient polymer reactions in artificial systems thus represents a long-standing objective in the fields of polymer and material science. Here, we show unprecedented macrocycle-metal-complex-catalyzed systems for efficient polymer reaction that result in 100 % transformation of the main chain functional groups presumably via a processive mode reaction. The complete polymer reactions were confirmed in not only intramolecular reaction (hydroamination) but also intermolecular reaction (hydrosilylation) by using Pd- and Pt-macrocycle-catalyzed systems. The most fascinating feature of the both reactions is that higher-molecular-weight polymers reach completion faster. Various studies suggested that the reactions occur in the catalyst cavity via the formation of a supramolecular complex between the macrocycle catalyst and polymer substrate like pseudorotaxane, which should be of characteristic of the efficient polymer reactions progressing in a processive mode.     

Supported Noble Metal Catalysts and Adsorbents with Soft Lewis Acid Functions

Heterogeneous noble metal catalysts exhibit various functions. Although their redox functions have been extensively studied, we focused on their soft Lewis acid functions. Supported Au, Pt, and Pd catalysts electrophilically attack the π-electrons of soft bases such as alkynes, alkenes, and aromatic compounds to perform addition and substitution reactions. Hydroamination, intramolecular cyclization of alkynyl carboxylic acids, isomerization of allylic esters, vinyl exchange reactions, Wacker oxidation, and oxidative homocoupling of aromatics are introduced based on a discussion of the active species and reaction mechanisms. Furthermore, the adsorption of sulfur compounds, which are soft bases, onto the supported AuNPs is discussed. The adsorption and removal of 1,3-dimethyltrisulfane (DMTS), which is the compound responsible for the stale odor of “hine-ka” in alcoholic beverages, particularly Japanese sake, is described.     

A facile method for generation of carbon oxide sulfide

Carbon oxide sulfide was easily generated upon heating of amine salts of carbamothioic acids at 85°C which were produced in situ from amines, carbon monoxide, and elemental sulfur in the presence of a catalytic amount of selenium under mild conditions.