Kinetics of thermal decomposition of MCO3 to MO (M=Ca,Sr and Ba)

The kinetics of the thermal decompositions of CaCO₃, SrCO₃ and BaCO₃ into their oxides were studied by thermogravimetry at constant and linearly increasing temperatures. The kinetics of the isothermal decompositions of calcium and strontium carbonates were described by the lawR _n =1–(1–)^1/n , wheren=1.8 and 1.2, respectively. The kinetics of the non-isothermal decompositions of the two carbonates, analysed by the Ozawa and Coats-Redfern methods, were in keeping with the isothermal kinetics. True kinetic compensation laws were established for each decomposition of the two carbonates, including the data under both isothermal and non-isothermal conditions.As concerns the decompositions of BaCO₃, however, there was some difference between the kinetic features relating the isothermal and non-isothermal conditions. A true kinetic compensation law was not established in this case.

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Zusammenfassung Die Kinetik der thermischen Zersetzung von CaCO₃, SrCO₃ und BaCO₃ zu den Oxiden wurden durch Thermogravimetrie bei konstanter und linear ansteigender Temperatur untersucht. Die Kinetik der isothermen Zersetzung von Calcium- und Strontium-carbonat folgt dem GesetzR _n =1–(1 –)^1/n, won=1,8 bzw. 1,2. Die Kinetik der nichtisothermen nach den Methoden von Ozawa und Coats-Redfern analysierten Zersetzung der zwei Carbonate ist in Übereinstimmung mit der isothermen Zersetzung. Wahre kinetische Kompensationsgesetze wurden für die Zersetzung der beiden Carbonate erhalten, einschließlich der sich sowohl auf isotherme als auch auf nichtisotherme Bedingungen beziehenden Daten. Was die Zersetzung von Bariumcarbonat betrifft, so wurden einige Unterschiede im kinetischen Verhalten bei der Zersetzung unter isothermen und nichtisothermen Bedingungen festgestellt. Ein wahres kinetisches Kompensationsgesetz konnte in diesem Falle nicht ermittelt werden.

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, . R _n =1–(1–)^1/n , , , 1,8 1,2. , -, . « » , . , , . - «» .

     

Reaction of selenobenzophenones with olefins. Formation of 1H-2-benzoselenopyrans. Reaction of 1H-2-benzoselenopyrans with diazoalkanes

Selenobenzophenone reacts as a diene with dimethyl acetylenedicarboxylate (DMAD) to lead to dimethyl 1H-1-diphenylmethyl-1-phenyl-2-benzoselenopyran-3,4-dicarboxylate (5c) in moderate yield; the initial [4 + 2] cycloaddition is followed by the addition of another 1 mol equiv of selenobenzophenone. The reaction might proceed through carbene insertion of the primary cycloadduct. On the other hand, 4,4'-dimethoxyselenobenzophenone combines as a diene with DMAD furnishing dimethyl 1H-1-p-methoxyphenyl-6-methoxy-2-benzoselenopyran-3,4-dicarboxylate (4a). The reaction of benzoselenopyran derivative (4) with diaryldiazomethanes afforded another type of carbene insertion product.     

On the thermodynamic stability and structural transition of clathrate hydrates

Gas mixtures of methane and ethane form structure II clathrate hydrates despite the fact that each of pure methane and pure ethane gases forms the structure I hydrate. Optimization of the interaction potential parameters for methane and ethane is attempted so as to reproduce the dissociation pressures of each simple hydrate containing either methane or ethane alone. An account for the structural transitions between type I and type II hydrates upon changing the mole fraction of the gas mixture is given on the basis of the van der Waals and Platteeuw theory with these optimized potentials. Cage occupancies of the two kinds of hydrates are also calculated as functions of the mole fraction at the dissociation pressure and at a fixed pressure well above the dissociation pressure.     

Chirality exchange from sp3 central chirality to axial chirality: benzannulation of optically active diaryl-2,2-dichlorocyclopropylmethanols to axially chiral alpha-arylnaphthalenes

Chirality exchange benzannulation of optically active (1S)-aryl(aryl')-2,2-dichlorocyclopropylmethanols (>99% ee) using TiCl4 successfully proceeded to give axially chiral (M)-alpha-arylnaphthalenes with excellent levels of stereo induction (>99% ee). This unique transformation involves the single-step chirality exchange from sp3 central chirality to axial chirality, that is, a type of excellent memory effect.     

Structural regulation of a peptide-conjugated graft copolymer: a simple model for amyloid formation

The self-assembly of peptides and proteins into beta-sheet-rich high-order structures has attracted much attention as a result of the characteristic nanostructure of these assemblies and because of their association with neurodegenerative diseases. Here we report the structural and conformational properties of a peptide-conjugated graft copolymer, poly(gamma-methyl-L-glutamate) grafted polyallylamine (1) in a water-2,2,2-trifluoroethanol solution as a simple model for amyloid formation. Atomic force microscopy revealed that the globular peptide 1 self-assembles into nonbranching fibrils that are about 4 nm in height under certain conditions. These fibrils are rich in beta-sheets and, similar to authentic amyloid fibrils, bind the amyloidophilic dye Congo red. The secondary and quaternary structures of the peptide 1 can be controlled by manipulating the pH, solution composition, and salt concentration; this indicates that the three-dimensional packing arrangement of peptide chains is the key factor for such fibril formation. Furthermore, the addition of carboxylic acid-terminated poly(ethylene glycol), which interacts with both of amino groups of 1 and hydrophobic PMLG chains, was found to obviously inhibit the alpha-to-beta structural transition for non-assembled peptide 1 and to partially cause a beta-to-alpha structural transition against the 1-assembly in the beta-sheet form. These findings demonstrate that the amyloid fibril formation is not restricted to specific protein sequences but rather is a generic property of peptides. The ability to control the assembled structure of the peptide should provide useful information not only for understanding the amyloid fibril formation, but also for developing novel peptide-based material with well-defined nanostructures.     

Characterization of amorphous hydrogenated carbon formed by low-pressure inductively coupled plasma enhanced chemical vapor deposition using multiple low-inductance antenna units

Three-dimensional plasma enhanced chemical vapor deposition (CVD) of hydrogenated amorphous carbon (a-C:H) has been demonstrated using a new type high-density volumetric plasma source with multiple low-inductance antenna system. The plasma density in the volume of phi 200 mm x 100 mm is 5.1 x 10(10) cm(-3) within +/-5% in the lateral directions and 5.2 x 10(10)cm(-3) within +/-10% in the axial direction for argon plasma under the pressure of 0.1 Pa and the total power as low as 400 W. The uniformity of the thickness and refractive index is within +/-3.5% and +/-1%, respectively, for the a-C:H films deposited on the substrates placed on the six side walls, the top of the phi 60 mm x 80 mm hexagonal substrate holder in the pure toluene plasma under the pressure is as low as 0.04 Pa, and the total power is as low as 300 W. It is also found that precisely controlled ion bombardment by pulse biasing led to the explicit observation in Raman and IR spectra of the transition from polymer-like structure to diamond-like structure accompanied by dehydrogenation due to ion bombardment. Moreover, it is also concluded that the pulse biasing technique is effective for stress reduction without a significant degradation of hardness. The stress of 0.6 GPa and the hardness of 15 GPa have been obtained for 2.0 microm thick films deposited with the optimized deposition conditions. The films are durable for the tribology test with a high load of 20 N up to more than 20,000 cycles, showing the specific wear rate and the friction coefficient were 1.2 x 10(-7) mm3/Nm and 0.04, respectively.     

Liquid crystalline properties and photochromism of 4-alkyl-N-(4-alkloxysalicylidene)anilines

Eight new homologous series of 4-alkyl-N-(4-alkloxysalicylidene)anilines were synthesized. The phase transitions of these homologues were determined using differential scanning calorimetry and polarizing optical microscopy. The homologues began to exhibit liquid crystalline phases as the terminal alkyl or alkoxyl chains were lengthened. In addition, some members of these homologues series exhibited photochromism in the solid state.     

The Effects of Sulphate and Tartrate Ions on the Molecular Organization of Water: Towards Understanding the Hofmeister Series (VI)

Using the 1-propanol (1P) probing methodology we have developed earlier, we characterized the effects of sulphate and tartrate anions on the molecular organization of H₂O. The results indicate that these two large anions belong to a new class of ??hydrophobe-like hydration center??. That is, sulphate and tartrate ions act as ??hydration centers?? with the hydration number 14±3 for both, and leave the bulk H₂O, away from hydration shells, unperturbed in the absence of the probing 1-propanol. As the mole fraction of the probe increases, however, the hydrogen bond probability of bulk H₂O away from hydration shells appears to decrease smoothly, as occurs with ??hydrophobes?? in H₂O. We plot the negative hydration number against the power to reduce the hydrogen bond probability of bulk H₂O for the two large anions. We also plotted the characteristic indices for ??hydrophiles?? and ??hydration centers?? whose characteristics we determined in the same manner earlier. H₂O defines the origin on this map. We found that a typical Hofmeister ranking for each anion matches reasonably well with that of the distance from the origin for each ion, in decreasing order starting from ions plotted in the north-west quadrant (representing the ??hydrophobe-like?? behavior) of the map and then in increasing order from the origin towards the south on the ordinate, the ??hydrophile-like?? behavior. These findings could be useful in understanding the Hofmeister series, pointing to the importance of the contribution made by the effect of each ion on H₂O, in addition to helping understand direct ion-protein interactions.     

Dynamical scaling analysis using the Lillie Number for vitrification of deeply supercooled glycerol

Thermal response was measured for a deeply supercooled glycerol specimen by applying calorimetric temperature scanning rate spectroscopy, cooling the specimen from liquid at a slow constant cooling rate until glass transition was observed. The effective fraction of glass as a function of temperature was determined and a new definition of glass transition temperature, T_gC, as the temperature at which the effective glass fraction to be 0.5 was presented. The relation between this and the cooling rate showed the Arrhenius behavior. The effective glass fraction curves shifted linearly as a function of ln(cooling rate). When T was scaled to the Lillie Number, the glass fraction lay on a master curve, which was successfully fitted with a Kohlrausch–Williams–Watts function. The Kohlrausch exponent, the relaxation time as a function of temperature and the kinetic fragility index were determined. The results were compared with literature values.     

Synthesis of Benzopyran-4-Amides Potassium Channel Openers Via Palladium-Catalyzed Amidation

The novel potassium channel openers benzopyran-4-amides have been synthesized via palladium-catalyzed amidation of 4-bromobenzopyrans under an atmoshere in the presence of an equivalent of potassium iodide.