o-Phenylene halocarbenonitrenes and o-phenylene chlorocarbenocarbene: a combined experimental and computational approach

[reaction: see text] Computations find that o-phenylene(halo)carbenonitrenes 2-XN, X = F, Cl, Br, have quinoidal singlet biradical ground states such as the parent o-phenylenecarbenonitrene (2-HN). Compared to the parent 2-HN, halogen substitution stabilizes the A' states relative to the A' ones. Halogen substitution also affects the barrier and exothermicity of the ring-opening reaction (to form unsaturated nitriles 4-XN, X = F, Cl, Br), but it has a smaller effect on the ring-closing reaction (to form benzo(aza)cyclobutadiene 3-XN, X = F, Cl, Br). Attempts to generate and observe the o-phenylene(halo)carbenonitrenes 2-XN, X = F, Cl, Br, using matrix isolation spectroscopy under conditions similar to those of the successful observation of 2-HN failed. Instead, the observed photoproducts were a mixture of 3-XN and 4-XN. In each case, the major product of the mixture appears to be the thermodynamically more stable one. In the case of X = Br, the observed mixture contains an additional component that is postulated to be Z-6-BrN. o-Phenylenechlorocarbenocarbene is also computed to have a quinoidal singlet biradical ground state and relatively stabilized A' excited states. Attempts to generate the biscarbene under matrix isolation conditions led to the detection of benzochlorocyclobutadiene (3-ClC), small amounts of the ring-open product (dienediyne 4-ClC), and cycloalkyne 5-ClC. Computations suggest that the formation of 5-ClC implies the generation of Z-6-ClC, which is analogous to the formation of Z-6-BrN from 2-BrN.     

Officinatrione: an unusual (17S)-17,18-seco-lupane skeleton,and four novel lupane-type triterpenoids from the roots of Taraxacum officinale

Novel 5 lupane-type of triterpenois, i.e., 3β-acetoxy-18α,19α-epoxylupan-21β-ol (1), 18α,19α-epoxy-21β-hydroxylupan-3-one (2), lup-18-ene-3,21-dione (3), lupa-18,21-dien-3β-yl acetate (4), and (17S)-17,18-seco-lup-19(21)-ene-3,18,22-trione (5), named officinatrione, as well as 16 known compounds from the roots of Taraxacum officinale collected in Takatsuki city, Osaka, Japan. Of the above compounds, 5 was the first lupane-type triterpene, of which the D-ring was open to form a nine-membered ring. Compounds 2 and 5 exhibited moderate cytotoxic activities against L1210 cell line (IC₅₀ 10.5 and 10.1 μM).     

Direct Asymmetric Mannich‐Type Reaction of α‐Isocyanoacetates with Ketimines using Cinchona Alkaloid/Copper(II) Catalysts

The enantioselective direct Mannich‐type reaction of ketimines with α‐isocyanoacetates has been developed. Excellent yields and enantioselectivity were observed for the reaction of various ketimines and α‐isocyanoacetates using cinchona alkaloid/Cu(OTf)₂ and a base. Both enantiomers of the products could be obtained by using pseudoenantiomeric chiral catalysts. This process offers an efficient route for the synthesis of α,β‐diamino acids.     

New phenylethanoid glycosides from Bacopa monniera

Three new phenylethanoid glycosides, viz. monnierasides I-III (1-3) along with the known analogue plantainoside B were isolated from the glycosidic fraction of Bacopa monniera. Their structures were elucidated mainly on the basis of two dimensional (2D) NMR spectral analyses.     

Synthesis of poly(ester amide)s by the melt polycondensation of semiaromatic polyesters with ethanolamine and their characterization

Semiaromatic poly(ester amide)s (PEAs) were synthesized by the melt polycondensation of ethanolamine (EA) derivatives with dimethyl terephthalate and ethylene glycol in the presence of tetrabutyl titanate as a catalyst, and their crystallization and thermal properties were investigated. The introduction of an amide group into a semiaromatic polyester such as poly(ethylene terephthalate) (PET) produced PEAs (EA-modified PET polymers) with an increase in the melting point. However, these PEAs were found to decompose at a lower temperature than PET on the basis of TGA. Moreover, direct pyrolysis/mass spectrometry measurements suggested that an initial step of the thermal decomposition was a β-CH hydrogen-transfer reaction via asix-member ring transition state at the ester–ethylene–amide unit, at which carbon–oxygen bond scission took place to yield carboxyl and N-vinylamide end groups. Furthermore, molecular orbital calculations using trimer models bis[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyl]terephthalate, N-[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyl]-4-[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyloxycarbonyl]benzamide, and N,N′-bis[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyl]terephthalamide strongly supported the idea that the β-CH hydrogen-transfer reaction in the thermal decomposition of PEAs might occur more easily at the methylene group next to the amide group in an ester–ethylene–amide unit rather than at the methylene group next to the ester group in an ester–ethylene–ester unit. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2184–2193, 2007     

An analysis of SEM techniques used to profile chemical etching on the semiconductor Hg1-xCdxTe

Various methods have been used to obtain accurate cross-sectional profiles of Hg_1-xCd_xTe devices after etching. Preliminary measurements from different etching techniques are also presented. Techniques used were scanning electron microscopy with stereo pairs and cleaved cross-sections, topography SEM (multiple detector SEM) and atomic force microscopy.     

An experimental investigation on isoclinic parameters in viscoelastoplastic materials under cyclic stresses

Photovisco-elastoplasticity has been developed and applied to various problems in nonlinear stress analysis as an extension of photoelasticity into nonlinear photomechanics. In photoelasticity, because stress is simply related to strain, isochromatics are proportional to either the principal stress difference or the principal strain difference and isoclinics indicate the directions of either principal stresses or principal strains separately. However, in photovisco-elastoplasticity, these optical responses are nonlinearly related to both stress and strain state simultaneously. Thus isochromatics are related nonlinearly with both the principal stress and strain differences. Isoclinics depend on the direction of principal strain as well as that of principal stress. Concerning now isoclinic parameter: according to the results of experiments performed by us for the deformation state where the directions of principal stress and strain do not coincide with one another, it has been found that isoclinic parameter moves gradually from the direction of principal stress to that of principal strain with increasing viscous deformation under constant stress. In the present research, extending our previous investigations, the behavior of isoclinic parameter has been examined experimentally under cyclic stressing, where the direction of principal stress changes alternately. In the course of an experiment, the variation of isoclinic parameter in relation to the number of cycles was measured together with the corresponding strain state on the thin-walled tubular specimen of celluloid softened by heating, subjected to combined loading conditions consisting of constant axial tension and cyclic torsion. The results obtained may be summarized as follows.

1. The cyclic-variation phase of isoclinic parameter lags behind the cyclic-variation phase of the direction of principal stress. The phase difference between these cyclic variations remains constant regardless of the number of cycles.
2. Isoclinic parameter has a value close to the direction of the principal stress within a range of a small number of cycles and decreases with an increase in the number of cycles. However, it does not approach the direction of principal strain but a value between the direction of the principal stress and that of the principal strain, with a certain constant ratio to them.

     

Radiator design for detecting high-energy neutrons with a nuclear track detector

Subsequent to the proposal of a two-layer structured radiator for more efficient detection of high-energy neutrons with a plastic nuclear track detector (PNTD), its availability has been investigated both experimentally and theoretically. An inner deuterized hydrocarbon (CD₂) layer adjacent to PNTD should play the role of both a radiator of deuterons recoiled there and a degrader for energetic protons recoiled in the outer layer of a CH₂ material. It was found that the energy dependence of the efficiency was changed sensitively by the thickness of the CD₂ layer. A best combination of CH₂ and CD₂ thickness was estimated under a condition of a constant total thickness. For example, the sensitivity could be flattened within 20% between about 5 and 70 MeV by using -CD₂ and -CH₂.