Facile synthesis of β-alkyl-substituted esters from α,β-unsaturated aldehydes

β-Alkyl-substituted carboxylates were synthesized in good yields from α,β-unsaturated aldehydes by using the 1:1 carbonyl adducts with diethyl bis (trimethylsilyl) phosphite.     

Synthesis of tris(β-diketonato) technetium(III) and its adsorption behaviour on silica gel

Tris (benzoylacetonato) technetium(III) and tris (2-thenoyltrifluoroacetonato) technetium(III) were synthesized by the direct reduction of pertechnetate with dithionite in the presence of excess ligands. The geometrical isomers of the benzoylacetonate were further separated by means of a silica gel column chromatography. In the silica gel system, the adsorption distribution coefficient of the tris (-diketonato) technetium(III) decreases in the order of Tc(acac)₃>fac-Tc(bzac)₃>mer-Tc(bzac₃)>Tc(tta)₃.     

Electrical and thermal properties in CuV2S4

The successive phase transitions of the cubic spinel structure CuV₂S₄ have been studied by the electrical resistivity and the specific heat. In the resistivity and the specific heat two anomalies have been observed at T₁～91 K and T₃≈55 K. The specific heat indicates that the phase transition at T₁ is in the vicinity of a tricritical point, where the resistivity has a small sharp peak. On the other hand, the specific heat shows a step at T₃, where a hysteresis of the resistivity indicates the existence of the first-order phase transition.     

Critical-point analysis of the two-phonon Raman spectrum of silicon

Two-phonon Raman spectrum of silicon has been measured in back-scattering configuration at room temperature using Argon ion laser. It reveals many critical points and consists mainly of two-phonon overtone states. The agreement between the calculated density of states from neutron diffraction data and the present Raman spectrum is excellent except the region where combination spectrum appears. Polarization measurement shows that the structure centered at 300 cm^?1 is not the one-phonon fine structure, predicted by Cowley and observed in part and identified as such by Wright and Mooradian, but the two-phonon overtone spectrum of acoustic phonons. Critical-point analysis has been done on the two-phonon overtone and combination spectra, and phonon frequencies of points of high symmetry in the Brillouin zone are determined and compared with other experimental results. In contrast to the Raman spectrum of diamond, no peak was observed near twice the frequency of zone-center optical phonon. This fact is explained by the difference of phonon dispersion relation between diamond and silicon.     

Synthesis and properties of aminoacylamido-AMP: chemical optimization for the construction of an N-acyl phosphoramidate linkage

This paper describes the design and synthesis of a new type of aminoacyl-adenylate analogue (aa-AMPN) having an N-acyl phosphoramidate linkage where the oxygen atom of the mixed anhydride bond of aminoacyl-adenylate (aa-AMP) is replaced by an amino group. This new type of aa-AMP analogue is expected to be useful as material for studies on the recognition mechanism of the aminoacylation of tRNA and other biochemical reactions. The condensation of phosphoramidite derivatives of carboxamides with nucleoside derivatives failed, because the activated phosphoramidite derivatives reacted with not only the hydroxyl groups but also another reactive species. An alternative approach was examined by the reaction of 5'-O-phosphoramidite adenosine derivatives with carboxamide derivatives. The TBTr and TSE groups were chosen for protection of the amino group of amino acid amides and the phosphate group, respectively. Detailed studies revealed that the use of 5-(3,5-dinitrophenyl)-1H-tetrazole as an activating catalyst of phosphoramidites resulted in rapid condensation within 10 min to give fully protected aa-AMPN derivatives. No side reaction occurred. Deprotection of these products via a two-step procedure gave aa-AMPN derivatives in good yields. It also turned out that aa-AMPNs thus obtained are stable under both acidic and basic conditions, such as 0.1 M HCl (pH 1.0) and 0.1 M NaOH (pH 13.0).     

Microexplosion of an emulsion droplet during Leidenfrost burning

An experimental study has been made of the microexplosion of an emulsion droplet on a hot surface during Leidenfrost burning. Photographic observation is used to study how the emulsion droplet behaves and what happens inside the droplet and to measure the waiting time for the onset of microexplosion. Weibull analysis was used to obtain the distribution function of the waiting time for the onset of microexplosion and to derive the formula for the rate of microexplosion as a function of water volume and emulsion temperature. The base fuels employed were n-decane, n-dodecane, n-tetradecane, and n-hexadecane. The results show that the increase in emulsion temperature with lapse of time results in the agglomeration and coalescence of microdroplets of base fuel dispersed in the continuous phase of water inside the emulsion droplet, terminated by the complete separation of the two phases. At the end of the phase separation process, an opaque water droplet is formed in the central core and is enveloped by the transparent shell of base fuel. Preferential evaporation of the base fuel occurs after the phase separation. The volume of the base fuel decreases while the water volume remains constant. The onset of the microexplosion of an emulsion droplet burning on the hot surface is classified by the wearout type of the Weibull distribution. The waiting time for the onset of the microexplosion decreases with increases in the normal boiling point of base fuel, initial water content, ambient pressure, and test surface temperature. The rate of microexplosion increases with the lapse of time and with increased normal boiling point of the base fuel. The rate of microexplosion increases linearly with increasing water volume in the emulsion droplet and decreases exponentially with the inverse of emulsion temperature.     

Autoignition and early flame behavior of a spherical cluster of 49 monodispersed droplets

Autoignition and early flame behavior of a spherical cluster of 49 monodispersed droplets in a high-temperature air were examined in microgravity. The monodispersed suspended-droplet cluster (MSDC) model with which both droplet spacing and initial droplet diameter were well-controlled was developed, and the solidified-fuel fiber-suspension technique was utilized for making the MSDC model. The tested 3D MSDC models had the HCP (hexagonal closest packing) structure. Individual flames, which enveloped each droplet, or group flame, which enveloped the whole droplet cluster, were formed immediately after ignition. The flame changed from the group flame to a cluster of the individual flames either with increasing the droplet spacing or decreasing the initial droplet diameter. Each of the individual flames merged into the group flame with the lapse of time. Burning sphere diameter decreased at the beginning, and then increased. The transition from the individual flames to the group flame occurred around the time period at which the burning sphere diameter reached its minimum. The time period at which the burning sphere diameter reached its maximum was delayed and the expansion rate of the burning sphere was enhanced with decreasing the droplet spacing or with increasing the initial droplet diameter.