Efficient partial hydrogenation of trichloromethyl to gem-dichloromethyl groups in platinum on carbon-catalyzed system

While gem-dichloromethyl groups can be directly synthesized by the mono-dechlorination of the corresponding trichloromethyl groups, the suppression control of the over-reduction to form chloromethyl or methyl functionalities is quite difficult. We have established the efficient and widely applicable mono-dechlorination method of the trichloromethyl groups to form the corresponding gem-dichloromethyl groups using platinum on carbon in dimethylacetamide as a specific solvent at 25 °C under a hydrogen atmosphere. The mono-dechlorination of the α,α,α-trichloromethylcarbonyl groups smoothly proceeded by the use of platinum on carbon as a catalyst in a highly chemoselective manner, while the efficient mono-dechlorination of the alkyl- and aryl-trichloromethyl groups required the combined use of Bu₃SnH.     

Garcinielliptone G from Garcinia subelliptica Induces Apoptosis in Acute Leukemia Cells

Cytotoxicity and apoptosis-inducing properties of compounds isolated from Garcinia subelliptica leaves were investigated. The hexane-soluble portion of MeOH extracts of G. subelliptica leaves that showed cytotoxic activity was separated to yield seven compounds 1–7. Chemical structure analysis using NMR spectroscopy and mass spectrometry confirmed that compound 1 was canophyllol, and compounds 2–7 were garcinielliptones N, O, J, G, F, and garcinielliptin oxide, respectively. Among them, garcinielliptone G (5) showed growth inhibition by causing apoptosis in THP-1 and Jurkat cells derived from human acute monocytic leukemia and T lymphocyte cells, respectively. Apoptosis induced by garcinielliptone G (5) was demonstrated by the detection of early apoptotic cells with fluorescein-labeled Annexin V and increases in cleaved caspase-3 and cleaved PARP protein levels. However, the addition of caspase inhibitor Z-VAD-FMK did not affect growth arrest or apoptosis induction. These results suggest that garcinielliptone G (5) can induce both caspase-3 activation and caspase-independent apoptosis. Therefore, garcinielliptone G (5) may be a potential candidate for acute leukemia treatment.     

The number of labeled graphs placeable by a given permutation

Let S be a finite set and σ a permutation on S. The permutation σ* on the set of 2-subsets of S is naturally induced by σ. Suppose G is a graph and V(G), E(G) are the vertex set, the edge set, respectively. Let V(G) = S. If E(G) and σ*(E(G)), the image of E(G) by σ*, have no common element, then G is said to be placeable by σ. This notion is generalized as follows. If any two sets of {E(G), (σ¹)*(E(G)),…,(σ^l−1)* (E(G))} have no common element, then G is said to be I-placeable by σ. In this paper, we count the number of labeled graphs which are I-placeable by a given permutation. At first, we introduce the interspaced Ith Fibonacci and Lucas numbers. When I = 2 these numbers are the ordinary Fibonacci and Lucas numbers. It is known that the Fibonacci and Lucas numbers are rounded powers. We show that the interspaced Ith Fibonacci and Lucas numbers are also rounded powers when I = 3. Next, we show the number of labeled graphs which are I-placeable by a given permutation is a product of the interspaced Ith Lucas numbers. Finally, using a property of the generalized binomial series, we count the number of labeled graphs of size k which are I-placeable by σ. © 1996 John Wiley & Sons, Inc.     

Study of the thermal degradability of poly(α-methylstyrene) with modified end groups

To induce degradabilities in polymers in response to environmental conditions, endm odification reactions of poly(α-methylstyrene) (PMS) derivatives were carried out. 2-Phenylallyl halide derivatives such as 2-phenylallyl bromide, 2-(p-tolyl)allyl bromide, and α-trifluoromethylstyrene were found to be suitable end-modification agents. For example, the ω-2-phenylallyl-PMS derivative was prepared with almost quantitative functionality by the reaction of the living PMS derivative with 2-phenylallyl bromide. In a similar way, ω-3,3-difluoro-2-phenylallyl- and ω-2-(4-toly)allyl-PMS derivatives were synthesized. Based on thermogravimetric analysis, the onset of the degradation temperature of the endmodified PMS derivatives decreased in the following order: ω-hydrogen- > ω-3,3-difluoro-2-phenylallyl- > ω-2-phenylallyl- > ω-2-(p-tolyl)allyl-PMS. Actually, the onset temperature of ω-2-(p-tolyl)allyl-PMS derivatives was 50°C lower than that of ω-H-PMS derivatives. These results indicate that the active species is produced effectively at the endunsaturated bond, which initiates depolymerization of the polymer at rather low temperatures. Therefore, it is concluded that a 2-phenylallyl substituent at the end of the PMS chain induces effective degradation through a radical mechanism.     

A hydrogel with rubber elasticity transition

Reaction between dimethyldivinylsilane and 3,6-diazaoctane in the presence of 3-lithio-3,6-diazaoctane yields a new telechelic oligomer, poly(silamine), which consists of alternating 3,3-dimethyl-3-silapentane and N,N′-diethylethylenediamine units in the main chain. Poly(silamine) shows unique phase transition properties in response to the degree of protonation of amino groups in the polymer. Poly(silamine) also shows a strong interaction with several anions. Due to the interaction between poly(silamine) and anions along with the protonation of amino groups in the poly(silamine), the rubber elasticity of poly(silamine) is drastically changed. A discrete volume change can be observed when the environmental pH of the poly(silamine) gels is varied. This can be explained not only by a change in ionic osmotic pressure but also by a change in the rubber elasticity of the networks in the gel.     

Simultaneous determination of silicate and phosphate in environmental waters using pre-column derivatization ion-pair liquid chromatography

A highly sensitive HPLC method for the simultaneous determination of soluble silicate and phosphate in environmental waters was developed, using ion-pair liquid chromatography preceded by the formation of their yellow α-heteropolymolybdates. The moderate-pH mobile phase enabled to use a highly efficient reversed-phase silica column. The pre-column coloring reactions at moderate-pH were reproducible for both silicate and phosphate in all quantification ranges with R.S.D.s less than 2% and 5%, respectively. The linear calibration lines between concentrations (mg-SiO₂/L and mg-PO₄/L) and peak area intensities were obtained for silicate and phosphate both with acceptable determination coefficients (r²) of 0.9999. The limits of determination for both analytes were 0.007 mg-SiO₂/L and 0.003 mg-PO₄/L, which were calculated theoretically using 10σ/slope. The four-digit dynamic ranges were obtained for 0.007-10 mg-SiO₂/L and 0.003-20 mg-PO₄/L. The developed method was applied for the analysis of tap water, river water, coastal seawater, well water, hot-spring water, commercial mineral water, and laboratory water. The results were very reasonable and acceptable from the environmental viewpoints, which were well correlated with those confirmed by the molybdenum-blue spectrophotometry.     

Changes of electrochemical responses of the bulk solution species by thermotropic permeability of liquid crystalline membranes coated on electrodes

Liquid crystalline/polymer composite membrane-coated electrodes were prepared by casting a 1,2-dichloroethane solution of N-(4-ethoxybenzylidene)-4′-n-butylaniline (EBBA) and polycarbonate (PC) on an electrode surface. The temperature-dependence of the permeability of the EBBA/PC composite membrane on electrodes to Fe(CN)^3?₆ ion as a solution-phase redox ion was investigated by means of hydrodynamic voltammetry at a rotating disk electrode. The permeability changed with temperature over the range of the crystalline-nematic-phase transition temperature of EBBA. It is demonstrated that the observed temperature-dependence of the permeability reflects the thermotropic properties of EBBA in the EBBA/PC composite membrane. Furthermore, the dependence of the limiting current of the steady-state current-potential curves for the reduction of Fe(CN)^—₆ at the EBBA/PC composite membrane-coated electrode upon the membrane thickness, the blend ratio of EBBA and PC and the concentration of Fe(CN)^3?₆ in a bulk solution was examined in order to understand the transport process of Fe(CN)^?3₆ through the EBBA/PC composite membrane from the membrane/solution interface to the electrode/membrane interface. The transport process of Fe(CN)^3?₆ within the membrane was found to obey Fick's Law.     

Magnetic and Crystallographic Properties of LnCrO4 (Ln=Nd, Sm, and Dy)

Zircon-type compounds LnCrO₄ (Ln=Nd, Sm, and Dy) were prepared. Their precise crystal structures at room temperature were determined from X-ray diffraction measurements. These compounds have a tetragonal system with space group I4₁/amd. Magnetic susceptibility and specific heat measurements have been performed for all the compounds in the temperature range between 1.8 and 300 K. For NdCrO₄, an antiferromagnetic transition was found at 25.2 K. SmCrO₄ and DyCrO₄ show magnetic transitions at 15.0 and 22.8 K, respectively. In addition, structural phase transitions were observed at 58.5 and 31.2 K, respectively. For DyCrO₄, the crystal structure below the transition temperature was determined by low-temperature powder X-ray diffraction measurements to be orthorhombic with space group Imma.     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.