Kinetic approach to partially overlapped thermal decomposition processes

Practical usefulness of the kinetic deconvolution for partially overlapped thermal decomposition processes of solids was examined by applying to the co-precipitated basic zinc carbonate and zinc carbonate. Comparing with the experimental deconvolutions by thermoanalytical techniques and mathematical deconvolutions using different statistical fitting functions, performance of the kinetic deconvolution based on an accumulative kinetic equation for the independent processes overlapped partially was evaluated in views of the peak deconvolution and kinetic evaluation. Two-independent kinetic processes of thermal decompositions of basic zinc carbonate and zinc carbonate were successfully deconvoluted by means of the thermoanalytical measurements in flowing CO₂ and by applying sample controlled thermal analysis (SCTA). The deconvolutions by the mathematical curve fittings using different fitting functions and subsequent formal kinetic analysis provide acceptable values of the mass-loss fractions and apparent activation energies of the respective reaction processes, but the estimated kinetic model function changes depending on the fitting functions employed for the peak deconvolution. The mass-loss fractions and apparent kinetic parameters of the respective reaction processes can be optimized simultaneously by the kinetic deconvolution based on the kinetic equation through nonlinear least square analysis, where all the parameters indicated acceptable correspondences to those estimated through the experimental and mathematical deconvolutions. As long as the reaction processes overlapped are independent kinetically, the simple and rapid procedure of kinetic deconvolution is useful as a tool for characterizing the partially overlapped kinetic processes of the thermal decomposition of solids.     

Ketonization of Secondary Hydroxy Groups of Alcohols and Diols with Hydrogen Peroxide Under the Influence of Tricetylpyridinium-12-Tungstophosphate

Molydbenum and tungsten-catalyzed oxidations of alcohols with dilute hydrogen peroxide under phase-transfer conditions have been focused in recent years 1–3. In a previous paper, we have reported that tricetylpyridinium-12-molybdophosphate(CMP), [π - C₅H₅N+(CH_{2 15}CH₃]₃ (PMO₁₂O₄₀)³-, prepared from 12-molybdophosphoric acid (MPA) and cetylpyridinium chloride (CPC), catalyzed the oxidation of secondary alcohols to carbonyl compounds with tert-butylhydroperoxide(t-BuOOH)⁴. When hydrogen peroxide in place of t-BuOOH was employed as the oxidant for the above oxidation, however, alcohols were oxidized with difficulty to give carbonyl compounds in poor yields. In continuation of this study, we wish to report here the selective oxidation of secondary hydroxy group of alcohols and diols and diols with H₂O₂ under the influence to tricetylpyridinium-12 tungstophosphate (CWP), [π-C₅H₅N+ (CH₂) 15 CH₃]₃(PW₁₂O₄₀)³-, derived from 12-tungstophosporic acid (WPA) and CPC.     

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).     

Additional cytotoxic substances isolated from the sponge-derived Gymnascella dankaliensis

A continuous investigation of secondary metabolites produced by the sponge-derived fungus, Gymnascella dankaliensis, has yielded a new polyketide tyrosine derivative, dankastatin C (3) and the known steroid, demethylincisterol A₃ (4), which was originally found from a Homaxinella marine sponge. The stereostructure of the new compound has been determined based on the analysis of 1D and 2D NMR data. Dankastatin C (3) showed potent cell growth inhibitory activity against the murine P388 cell line.     

Conductive liquid crystalline compounds having a piperazine structure

New conductive thermotropic liquid crystalline materials having a piperazine ring in the central core: 1-[4-(9-decenyloxy)phenyl]-4-alkylpiperazines (6) were synthesized. The mesomorphic behaviours of these compounds and their conductivity in the liquid crystal phase were measured. The principal features of these compounds are to exhibit a smectic B phase around room temperature (for example 6: Cr 50 SmB 81 I, °C) and to exhibit a large dark current (6d: 430 μA cm^?2, applied voltage 20 V, at 70°C) in the smectic B phase.     

Visualizing Hepatic Copper Release in Long–Evans Cinnamon Rats Using Single-Photon Emission Computed Tomography

The potential utility of an imaging agent for the detection of hepatic copper was investigated in a Wilson’s disease animal model. Solid-phase peptide synthesis was used to construct an imaging agent which consisted of a copper-binding moiety, taken from the prion protein, and a gamma ray-emitting indium radiolabel. Long–Evans Cinnamon (LEC) rats were used for the Wilson’s disease animal model. Our evaluation methodology consisted of administering the indium-labeled agent to both LEC and genetically healthy Long–Evans (LE) cohorts via a tail vein injection and following the pharmacokinetics with single-photon emission computed tomography (SPECT) over the course of an hour. The animals were then sacrificed and their livers necropsied. An additional control agent, lacking the copper-binding moiety, was used to gauge whether any change in the hepatic uptake might be caused by other physiological differences between the two animal models. LEC rats injected with the indium-labeled agent had roughly double the amount of hepatic radioactivity as compared to the healthy control animals. The control agent, without the copper-binding moiety, displayed a hepatic signal similar to that of the control LE animals. Additional intraperitoneal spiking with CuSO₄ in C57BL/6 mice also found that the pharmacokinetics of the indium-labeled, prion-based imaging agent is profoundly altered by exposure to in vivo pools of extracellular copper. The described SPECT application with this compound represented a significant improvement over a previous MRI application using the same base peptide sequence.     

Synthesis of Methyl (Methyl D-and L-Idopyranosid)Uronates from myo-Inositol

Abstract

Methyl (methyl α-D-(9a), α-(9b), β-D-(10a), and β-L-(10b) idopyranosid)uronates were synthesized from myo-inositol. Baeyer-Villiger oxidation of the optically resolved inosose derivatives (3a and 3b) proceeded regioselectively to afford 4a and 4b in high yields, respectively. Ring-opening of the 7-membered hemiacetal-lactones (4a and 4b) with acid and subsequent deprotection gave the title compounds.     

Fluorinated and Trifluoromethylated Corannulenes

The syntheses and properties of corannulenes carrying electron‐withdrawing groups (F, CF₃, C₆F₅) are reported. Direct fluorination of corannulene (C₂₀H₁₀) was carried out with xenon difluoride, and the crystal structure of the product was confirmed by the X‐ray analysis. Novel trifluoromethylated corannulenes, including the versatile 4,9‐dibromo‐1,2‐bis(trifluoromethyl)corannulene, were obtained by various established ring‐closing reactions. Besides the use of hexafluorobutyne for the construction of fluoranthenes by Diels–Alder reaction as precursor molecules to form 1,2‐disubstituted corannulenes, bis(pentafluorophenyl)acetylene was employed as dienophile. The molecular structure and crystal packing of a trifluoromethylated corannulene was determined by single‐crystal X‐ray analysis and compared with those known brominated and trifluoromethylated corannulenes. The general electron‐acceptor properties of corannulenes bearing substituents introduced in particular positions by liquid‐phase synthesis are discussed together with published computational results.     

7,7,8,8‐Tetraaryl‐o‐quinodimethane Stabilized by Dibenzo Annulation: A Helical π‐Electron System That Exhibits Electrochromic and Unique Chiroptical Properties

When two benzene rings are fused to a tetraaryl‐o‐quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron‐donating alkoxy groups, 1 undergo reversible two‐electron oxidation to 2 ²⁺, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec‐butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b ²⁺ and 2 c ²⁺, which represents an efficient method for enhancing circular‐dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X‐ray analysis of dication 2 ²⁺ revealed π–π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response.