Polymorphism of POP and SOS III. Solvent crystallization of β2 and β1 polymorphs

Single crystals of β₁ and polycrystals of β₂ of POP and SOS were obtained from acetonitrile solution. The crystallization behavior of the two polymorphs was almost the same in POP and SOS; rapid cooling of the solution preferentially crystallized the metastable β₂ form, and the most stable β₁ form crystallized in a very low solute concentration at the expense of β₂, via solution-mediated transformation. The single crystal of β₂ revealed needle-like irregular shape, whereas well-defined slender rhombic shape was observed in β₁. The solubilities of the β₁ forms of POP and SOS in tetradecane solution were precisely measured in a temperature range of 10∼20°C. This study showed that the solvent crystallization was the single way to grow the β₁ crystal, since melt-cooling and melt-mediated transformation did not crystallize β₁ both in POP and SOS. Presented at 1988 AOCS Annual Meeting at Phoenix.     

Polymorphic behavior of gondoic acid and phase behavior of its binary mixtures with asclepic acid and oleic acid

Molecular properties of polymorphic forms of gondoic acid [cis-C_20:1Δ11ω9 (GOA)] have been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), optical microscopy, and Raman scattering, in comparison to those of six principal unsaturated fatty acids: oleic acid [cis-C_18:1Δ9ω9 (OA)], erucic acid [cis-C_22:1Δ13ω9 (ERA)], petroselinic acid [cis-C_18:1Δ6ω12 (PSA)], asclepic acid [cis-C_18:1Δ11ω7 (APA)], palmitoleic acid [cis-C_16:1Δ9ω7 (POA)], and elaidic acid [trans-C_18:1Δ9ω9 (ELA)]. In addition, phase behavior of binary mixtures of GOA and APA and OA was examined by XRD and DSC. The polymorphic structures of GOA are quite similar to those of APA, ERA, POA, and partly to OA. In particular, DSC and Raman scattering studies have shown that gondoic acid exhibits conformational disordering on heating at the ω-chain, a chain segment between the double bond and CH₃ group, as a transition from all-trans (γ form) to gauche-rich (α form) conformations. A miscible mixing phase was observed in the mixture of GOA and APA, yet eutectic phases were observed in the GOA and OA mixtures. This is a remarkable contrast because the binary mixture systems of varying combinations of cis-unsaturated fatty acids examined so far exhibited either eutectic nature or molecular compound formation. It is expected that specific molecular interactions between GOA and APA that originate from the equivalence of the length of the Δ-chain, the chain segment between the cis-double bond and COOH group, and also from the presence of the γ-α order-disorder transformation would be operating to form the miscible mixing phase.     

Photocatalysts using hexa- and octa-titanates with different tunnel space for water decomposition

Photocatalytic activities for water decomposition were examined for photocatalysts using hexa- and octa-titanates and TiO2(B) with different tunnel space in the structure. Using RuO2 as promoter, M2Ti6O13 (M = Li, Na, K, Rb) showed the stoichiometric production of Hz and O₂ except for Li, whereas H₂Ti₈O₁₇ and TiO₂(B) had very low activity producing only hydrogen as a product. The effects of promoters on Na₂Ti₆O₁₃ showed that the activity increased in the order of RuO₂ > RuO₂ + IrO₂ > IrO₂ > RuO₂ + Pt > MnO₂. These effects along with other related ones are discussed: it emerges that the presence of the tunnels is important for the achievement of high photocatalytic activity.     

New type of tin support for hydroprocessing catalyst

TiN supported molybdenum sulfide catalysts showed much higher activity for cleavage of C-C bonds than oxide supported molybdenum sulfide catalysts, indicating the possibility of a new generation of supports for hydroprocessing catalysts.     

Chaos in parametric resonance flow at water-mercury interface

In the electrochemical system with liquid-liquid interface, intense local convections by the resonance with potential pulses take place. Therefore, with laser beam scattering, temporal movement of the water-mercury interface was observed. As a result, the scattering efficiency showed non-linear oscillation.

Such non-linear response could be controlled by potential pulse height. As the potential height was increased, new scattering peaks in the oscillation emerged, which was expected of a kind of bifurcation phenomenon. From these results, phase portrait, Poincarè section, correlation dimension of the strange attractor and the largest Lyapunov exponent of the trajectories were obtained. Consequently, it was concluded that all the parameters indicate chaotic behavior of the resonance flow.     

Low-temperature selective reduction of NO with propene over alkaline-exchanged mordenites

Partially protonated alkaline mordenites showed higher activity per acid amount below 573 K than acidic zeolites for the selective reduction of NO with C₃H₆ in the presence of O₂, which can be related to a high concentration of NO₃ ^- species in the zeolite channels. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effects of amino acid replacements around the reactive site of chicken ovomucoid domain 3 on the inhibitory activity toward chymotrypsin and trypsin

We have previously shown that replacing the P1-site residue(Ala) of chicken ovomucoid domain 3 (OMCHI3) with a Met or Lysresults in the acquisition of inhibitory activity toward chymotrypsinor trypsin, respectively. However, the inhibitory activitiesthus induced are not strong. In the present study, we introducedadditional amino acid replacements around the reactive siteto try to make the P1-site mutants more effective inhibitorsof chymotrypsin or trypsin. The amino acid replacement AspTyrat the P2' site of OMCHI3(P1Met) resulted in conversion to a35000-fold more effective inhibitor of chymotrypsin with aninhibitor constant (K_i) of 1.17x10^–11 M. The K_i valueof OMCHI3(P1Met, P2'Ala) indicated that the effect on the interactionwith chymotrypsin of removing a negative charge from the P2'site was greater than that of introducing an aromatic ring.Similarly, enhanced inhibition of trypsin was observed whenthe AspTyr replacement was introduced into the P2' site of OMCHI3(P1Lys).Two additional replacements, AspAla at the P4 site and ArgAlaat the P3' site, made the mutant a more effective inhibitorof trypsin with a K_i value of 1.44x10^–9 M. By contrast,ArgAla replacement at the P3' site of OMCHI3(P1Met, P2'Tyr)resulted in a greatly reduced inhibition of chymotrypsin, andAspAla replacement at the P4 site produced only a small changewhen compared with a natural variant of OMCHI3. These resultsclearly indicate that not only the P1-site residue but alsothe characteristics, particularly the electrostatic properties,of the amino acid residues around the reactive site of the proteaseinhibitor determine the strength of its interactions with proteases.Furthermore, amino acids with different characteristics arerequired around the reactive site for strong inhibition of chymotrypsinand trypsin.     

One-step formation of ethyl methyl ketone from 1-butene and water on ultrastable Y-type zeolite catalyst

Proton exchanged ultrastable Y-type zeolite with silica/alumina = 40 showed a pronounced catalytic activity for the formation of ethyl methyl ketone directly from 1-butene and water. The formation rate of ethyl methyl ketone was much higher than those on MoO₃-based catalysts in the oxidation of 1-butene by oxygen. It was suggested that the basic site necessary for the formation of ethyl ketone directly from 1-butene and water would be the pentacoordinated Al.     

Thermal decomposition of uranium peroxide hydrates

The thermal decomposition of uranium peroxide hydrates, UO₄·4H₂O and UO₄·2H₂O, has been investigated by thermal analyses, X-ray diffraction study and infrared spectroscopy. As a result, it is concluded that the thermal decomposition of uranium peroxide hydrates proceeds in the following sequence: where 3 ≤ x ≤ 3.5.     

Preparation of gelatinous aluminium hydroxide by urea from aqueous solutions containing chloride,nitrate and sulphate of aluminium

The preparation of gelatinous aluminium hydroxide from aqueous solutions containing a mixture of the chloride, nitrate or sulphate of aluminium and urea by heating at 95°C has been investigated under different conditions. The pH value of aqueous solutions, on heating for a given period of time, gradually increases, rises steeply at pH 4.0–7.5 and finally approaches a constant value. The precipitate appears at about pH 7 in the presence of chloride or nitrate ions and about pH 4 in the presence of sulphate ions. Although the gelatinous precipitates in the chloride and nitrate systems are apparently different from the granular, filterable one in the sulphate system, their compositions are not influenced by the species of aluminium salt. The fresh precipitates exist in an amorphous state, and go to pseudoboehmite by ageing. It seems that the amount of pseudoboehmite increases as the concentration of aluminium salt in aqueous solution decreases. However, the transformation from amorphous aluminium hydroxide to pseudoboehmite is reduced in the presence of sulphate ions. Furthermore, it is found that the X-ray diffraction peak for the (200) plane, as an orthorhombic structure, in the pseudoboehmite precipitated from chloride or nitrate solution is more intense than that from sulphate solution.