Novel photolytic decomposition method of organic compounds with a high output low-pressure mercury lamp for voltammetric trace metal analysis

A high output low-pressure mercury lamp, 400 W L-Hg, was successfully used for the photolytic decomposition of dissolved oganic compounds as the pretreatment for the determination of trace metal ion in aqueous solution by stripping voltammetry. Various amino acids, showing interferences on voltammetric determination of metal ions, can be removed quite easily by intensive UV irradiation at room temperature. Effect of pH, concentration of electrolyte and dissolved oxygen on the efficiency of photolysis are also described. This method uses no additional chemicals such as acids or oxidants and can be carried out in closed clean conditions.     

Base-catalyzed stereoselective isomerization of electron-deficient propargylic alcohols to E-enones

We have developed highly stereoselective methods to isomerize electron-deficient propargylic alcohols to E-enones under mild conditions (EWG = electron-withdrawing group). Among weak bases we screened, catalytic (10-20 mol %) 1,4-diazabicyclo[2.2.2]octane (DABCO) was found to be effective in most cases. When the substrate is conjugated with an amide, the addition of sodium acetate catalyzed the isomerization.     

On the mechanism of DABCO-catalyzed isomerization of gamma-hydroxy-alpha,beta-alkynoates to gamma-oxo-alpha,beta-(E)-alkenoates

[reaction: see text] Since the discovery of organic base-catalyzed isomerization of gamma-hydroxy-alpha,beta-acetylenic esters to gamma-oxo-alpha,beta-trans-alkenyl esters in 1949, the mechanism has not been elucidated. This study shows that the mechanism involves cumulene formation, protonation with the conjugate acid of the amine, and protonation of the resulting allenol with water.     

A highly sensitive fluorescence method reveals the presence of palladium in a cross-coupling reaction mixture not treated with transition metals

We previously reported a Suzuki–Miyaura coupling in dimethyl carbonate without adding additional transition metals. Here, we show an analysis of the reaction mixture that revealed the presence of palladium using a fluorogenic Tsuji–Trost reaction.     

Generalization of uncertainty relation for quantum and stochastic systems

The generalized uncertainty relation applicable to quantum and stochastic systems is derived within the stochastic variational method. This relation not only reproduces the well-known inequality in quantum mechanics but also is applicable to the Gross–Pitaevskii equation and the Navier–Stokes–Fourier equation, showing that the finite minimum uncertainty between the position and the momentum is not an inherent property of quantum mechanics but a common feature of stochastic systems. We further discuss the possible implication of the present study in discussing the application of the hydrodynamic picture to microscopic systems, like relativistic heavy-ion collisions.     

Ion-pair formation between Cd(II), Na(I), and Ag(I) complex ions with 18-crown-6 ether derivatives and various pairing anions in water: an understanding of the ion-pair formation based on the HSAB principle

The ion-pair formation constants (K(MLX)(0)/mol(-1) dm(3)) of CdL(2+) with Br(-) or NaL(+) with N,N-diethyldithiocarbamate ion (DDTC(-)) in water were determined potentiometrically at 25°C; ionic strength (I)→0: L denotes 18-crown-6 ether (18C6) and its mono-benzo derivative for the CdBr(2)-L system and 15-crown-5 ether and 18C6 for the NaDDTC-L one. The formation constant corresponding to the simple salt, NaDDTC, in water was also determined at I→0. Using the log K(CdLX)(0) values of CdLCl(+), CdLBr(+), CdLPic(+), and CdLSO(4), then CdL(2+) and picrate ion (Pic(-)) in water have been classified with the hard and soft acids and bases principle, where the values were available in the literature, except for CdLBr(+). The same classification was examined in NaX-L systems with X(-) = DDTC(-), trifluoroacetate ion, MnO(4)(-), ReO(4)(-), Pic(-), and BPh(4)(-) and the AgPic-L one. Consequently, CdL(2+), NaL(+), and AgL(+) were classified as the hard acids, while Pic(-) and BPh(4)(-) as the hard bases. These results reflected the reactivities of the complex ions in ion-pair formation with X(-) and SO(4)(2-) in water.     

Structural requirements for the antiproliferative activity of pre-mRNA splicing inhibitor FR901464

FR901464, a natural product isolated from a bacterium source, activates a reporter gene, inhibits pre-mRNA splicing, and shows antitumor activity. We previously reported the development of a more potent analogue, meayamycin, through the total synthesis of FR901464. Herein, we report detailed structure-activity relationships of FR901464 that revealed the significance of the epoxide, carbon atoms in the tetrahydropyran ring, the Z geometry of the side chain, the 1,3-diene moiety, the C4-hydroxy group, and the C2'-carbonyl group. Importantly, the methyl group of the acetyl substituent was found to be inessential, leading to a new potent analogue. Additionally, partially based on in vivo data, we synthesized and evaluated potentially more metabolically stable analogues for their antiproliferative activity. These structural insights into FR901464 may contribute to the simplification of the natural product for further drug development.