New cytotoxic diterpenes from rondeletia panamensis (rubiaceae)

From the wood stem and stem bark of the Panamanian plant Rondeletia panamensis (Rubiaceae), three novel diterpenes have been isolated. The structure of oxidopanamensin (2) was determined by single crystal X-ray crystallography of the diacetate derivative. Panamensin (4) was correlated with oxidopanamensin (2) by epoxidation under alkali conditions and with rondeletin (6) by hydrogenation to 14,15-dihydrorondeletin (8). Of the three isolates, panamensin (4) and oxidopanamensin (2) were cytotoxic in the KB test system but rondeletin was inactive.     

Computations and Stability of the Fukui Invariant

T. Fukui introduced an invariant for the blow-analytic equivalence of real singularities. For a nondegenerate analytic function (germ) f, he discovered a formula for computing the one-dimensional invariant, denoted by A(f) := A ₁(f). We find a formula for A(f) for any f (real or complex, degenerate or not). We then define, and characterise, various notions of stability of A(f), using the formula. For real analytic f, the Fukui invariant with sign is defined, and computed by a similar formula. In the case where f is an analytic function of two complex variables, A(f) can also be computed using the tree-model of f.     

Poly(benzyl ether) dendrimers with strongly fluorescent distyrylbenzene cores as the fluorophores for peroxyoxalate chemiluminescence: insulating effect of dendritic structures on fluorescent sites

Poly(benzyl ether) dendrimers containing strongly fluorescent distyrylbenzene cores were synthesized, and their fluorescence and electrochemical properties as well as the action as fluorophores in the chemiluminescence reactions were investigated. While all the dendrimers exhibited almost the same properties except for their intensities, a characteristic feature due to the dendritic structure was observed in the electrochemical behaviors. In the peroxyoxalate chemiluminescence reactions using these dendrimers as fluorophores, a bimolecular interaction between the high-energy intermediates and fluorophores was established, and a decrease in the chemiluminescence intensity with an increasing generation was observed, which was connected with the insulating effect of the dendritic structures on the core.     

Preparation of arsenic‐containing white rice grains as calibration standards for X‐ray fluorescence analysis of total arsenic in cereals

A preparation method of arsenic‐containing white rice grains as calibration standards was developed for the X‐ray fluorescence (XRF) analysis of arsenic in rice grains. Calibration standards were prepared by adding 10 g of white rice grains (from Japan) to 100 ml methanol‐containing dimethylarsinic acid corresponding to 2–100 µg arsenic. The mixture was heated, dried at 150 °C, cooled to room temperature, and then stored in a silica gel desiccator. A total of 5.0 g of each calibration standard was packed into a polyethylene cup (32 mm internal diameter and 23 mm height) covered with a 6‐µm‐thick polypropylene film and then analyzed by wavelength‐dispersive XRF spectrometry. The calibration curve for arsenic obtained from the white rice grains containing arsenic showed good linearity over a concentration range of 0.21–5.00 mg kg^?1 arsenic. The limit of detection of arsenic was 0.080 mg kg^?1. To check the reliability of the XRF method, the concentrations of arsenic in six samples of grain cereals and two samples of flour were compared with those obtained by atomic absorption spectrometry after acid decomposition. The values obtained by both analytical methods showed good agreement. Copyright © 2016 John Wiley & Sons, Ltd.     

Mössbauer and XRD analysis of corrosion products on weathering steel treated by wet-dry cycles using various solutions

Weathering steels (COR-TEN) were corroded by wet-dry cycles using a splay of various solutions in a laboratory. Corrosion products on weathering steel were characterized by X-ray diffractometry and Mössbauer spectrometry at room and low temperatures. Fine α-FeOOH, γ-FeOOH and γ-Fe ₂ O ₃ are fundamentally formed in various atmospheric conditions. β-FeOOH is additionally formed under the existence of chloride ions, but not formed when sulfate ions are coexisting. Spraying a NaF solution prevents the progress of corrosion.     

Development of an efficient photocatalytic system for CO2 reduction using rhenium(I) complexes based on mechanistic studies

The reaction mechanism of photocatalytic CO2 reduction using rhenium(I) complexes has been investigated by means of a detailed comparison of the photocatalyses of three rhenium(I) complexes, fac-[Re(bpy)(CO)3L] (L = SCN- (1-NCS), Cl- (1-Cl), and CN- (1-CN)). The corresponding one-electron-reduced species (OER) of the complexes play two important roles in the reaction: (a) capturing CO2 after loss of the monodentate ligand (L) and (b) donation of the second electron to CO2 by another OER without loss of L. In the case of 1-NCS, the corresponding OER has both of the capabilities in the photocatalytic reaction, resulting in more efficient CO formation (with a quantum yield of 0.30) than that of 1-Cl (quantum yield of 0.16), for which OER species have too short a lifetime to accumulate during the photocatalytic reaction. On the other hand, 1-CN showed no photocatalytic ability, because the corresponding OER species does not dissociate the CN- ligand. Based on this mechanistic information, the most efficient photocatalytic system was successfully developed using a mixed system with fac-[Re(bpy)(CO)3(CH3CN)]+ and fac-[Re{4,4'-(MeO)2bpy}(CO)3{P(OEt)3}]+, for which the optimized quantum yield for CO formation was 0.59.     

Chemistry of polycarbon species: from clusters to molecular devices

Polycarbon species with pi-conjugated systems interact with attached metal fragments to exhibit a variety of intriguing structural features and chemical properties. In this Perspective, following an introductory account of polycarbon cluster compounds and the unique chemical transformations on them which cannot easily be realized by mononuclear species, the properties of polynuclear complexes connected by pi-conjugated carbon-rich bridging ligands will be discussed with emphasis on those applicable to molecular electronics, e.g. wire-like behavior (molecular wires), higher dimensional systems (branch circuits), and switching functions.