Comparison of the relative stability of pharmaceutical cocrystals consisting of paracetamol and dicarboxylic acids

Objective: The aim of this study is to evaluate the relative stability of pharmaceutical cocrystals consisting of paracetamol (APAP) and oxalic acid (OXA) or maleic acid (MLA).

Significance: These observations of cocrystal stability under various conditions are useful coformer criteria when cocrystals are selected as the active pharmaceutical ingredient in drug development.

Method: The relative stability was determined from the preferentially formed cocrystals under various conditions.

Result: Cocrystal of APAP–OXA was more stable than that of APAP–MLA in a ternary cogrinding system and possessed thermodynamical stability. On the other hand, when grinding with moisture or maintaining at high temperatures and relative humidity conditions, APAP–MLA was more stable, and OXA converted to OXA dihydrate. In the slurry method, APAP–OXA was more stable in aprotic solvents because the APAP–OXA with low-solubility product precipitated.

Conclusions: The relative stability order was affected by preparing conditions of presence of moisture. This order might attribute to the small difference of crystal structure in the extension of the hydrogen bond network.     

A small three-way valve using particle excitation with piezoelectric transducers for hydraulic actuators

Abstract

Robots composed of hydraulic actuators have been utilized in various fields and at disaster sites. However, the hydraulic control system for multiple-degree-of-freedom mechanisms is large because such systems require many control components. The purpose of this research was to develop a small hydraulic flow control valve. This paper describes the fabrication and evaluation of a small three-way valve by particle excitation using a piezoelectric transducer. This valve consists of two transducers and can switch the inlet and outlet ports by applying an AC voltage of different driving frequencies to each transducer because each transducer has different resonant frequencies. The flow rate was controlled by applying a voltage to the piezoelectric transducer. We evaluated the vibration characteristics of the fabricated three-way valve. The vibration velocity exhibited peaks at 120 and 155 kHz for the inlet and outlet port, respectively, and that of each transducer increased with the applied voltage. Therefore, this three-way valve can switch the opening port by changing the driving frequencies and continuously controlling the flow rate. As a result, we have succeeded in driving the novel small three-way valve.     

Intermediate hydrocarbon species for the CO2-CH4 reaction on supported Ni catalysts

By using pulse surface reaction rate analysis (PSRA), the detailed structure of the intermediate hydrocarbon species was revealed by measuring the dynamic behavior of both CO and H₂ produced from the CO₂-CH₄ reaction on supported Ni catalysts. It was found that the number of hydrogen atoms involved in the intermediate was different from one catalyst support to another: 2.7 for MgO, 2.5 for ZnO, 2.4 for Al₂O₃,1.9 for TiO₂, and 1.0 for SiO₂.     

Pt-Al2O3 Cryogel with High Thermal Stability for Catalytic Combustion

The cryogel catalyst of platinum on alumina was prepared from aluminum sec-butoxide and H₂PtCl₆ through the sol-gel technique and subsequent freeze drying. The cryogel catalyst showed higher thermal stability of platinum than the corresponding xerogel or impregnation catalysts, which was ascribed to the more intimately developed platinum-alumina interaction accompanied by the encapsulation of the metal into the alumina cryogel. It was also shown that platinum accessibility was higher on the cryogel than on the xerogel despite the higher thermal stability of the metal on the formed than on the latter. For the VOC combustion, the cryogel exhibited higher activity than the xerogel and impregnation catalysts. Also for the methane combustion the cryogel showed higher activity, although it showed lower activity than the impregnation catalysts above 600 °C. By the addition of ceria as an additive to the cryogel catalyst, the CH₄ combustion activity was improved especially in the temperature region above 600 °C.     

Distribution, diversity and regulation of alcohol oxidase isozymes, and phylogenetic relationships of methylotrophic yeasts

In this study, we attempted to classify the methylotrophic yeasts based on diversities of alcohol oxidase (AOD), i.e. zymogram patterns and partial amino acid sequences. According to zymogram patterns for AOD, members of the methylotrophic yeasts separate into two major lineages, one group involving strains having a single AOD and the other group, including Pichia methanolica, Candida pignaliae and C. sonorensis, showing nine AOD isozymes. Based on partial amino acid sequences of AOD, the methylotrophic yeasts could be divided into five groups, and this classification agrees mostly with grouping based on 26S domain D1/D2 rDNA nucleotide sequences, except for some strains. Moreover, the strains having AOD isozymes constitute one group with P. trehalophila, P. glucozyma and Pichia sp. strain BZ159, although these strains are divided into two types, based on amino acid sequences of second AODs. On the other hand, these AOD isozymes consist of two subunits; the first subunits are induced not only by methanol but also by glycerol and pectin, although the second subunits are mainly induced by methanol. These data indicate that AOD isozymes and second AOD genes distribute widely in several methylotrophic yeasts in the natural environment, and second AOD genes may have evolved as methylotrophic genes that can adapt to the environmental conditions of higher methanol concentrations.     

Crystal, electronic and luminescence properties of Eu-doped Sr2Al2−xSi1+xO7−xNx

The crystal and electronic structures, as well as the luminescence properties of Sr₂Al_2−xSi_1+xO_7−xN_x:Eu²⁺ are reported. First-principles calculations energetically confirm that the Al and Si atoms are in partial ordering in the 2a and 4e sites in Sr₂Al₂SiO₇. In addition, the band structure calculation shows that Sr₂Al₂SiO₇ has an indirect band gap with an energy gap of about 4.07 eV, which is in good agreement with the experimental data (5.3 eV) obtained from the diffuse reflection spectrum. The crystal structure of Sr₂Al₂SiO₇ can be modified by Si–N substitution for Al–O in the lattice with a maximum solubility of about x=0.6. The average bond length of Eu_Sr^-(O,N) slightly increases although the lattice parameters decrease with the incorporation of Si–N in Sr₂Al₂SiO₇:Eu²⁺. Under excitation in the visible spectral region, Sr₂Al_2−xSi_1+xO_7−xN_x:Eu²⁺ emits blue to yellow light with a broad emission band in the range of 480–570 nm, varying with both the Eu concentration and the x value. The red shift of the emission band of Eu²⁺ is associated with an increase in the crystal-field splitting and the covalency, which arise from the incorporation of nitrogen as well as the energy transfer between the Eu ions at high Eu concentrations. Moreover, the Eu ions have a strong effect on both the concentration quenching and the thermal quenching in Sr₂Al_2−xSi_1+xO_7−xN_x. The temperature dependence of photoluminescence indicates that Sr₂Al_2−xSi_1+xO_7−xN_x:Eu²⁺ shows strong thermal quenching due to the dominant nonradiative process at room temperature.     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index

The effects of the volume and pH of the impregnation solution and of the calcination conditions were examined on the physicochemical and catalytic properties of a 13 wt% MoO₃/Al₂O₃ extrudate catalyst. The Al₂O₃ support and drying procedures (static conditions without flowing air) were fixed in the preparations. In the present series of catalysts, the amount of crystalline MoO₃ was marginally small. It was found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased, gradually approaching a maximum value. The increase in pH (2–8) of the impregnation solution was found to reduce the dispersion of Mo oxide species. The Mo dispersion increased slightly for the impregnation catalysts as the calcination temperature increased (673–873 K), whereas it decreased for the equilibrium adsorption catalysts. The effects of the calcination atmosphere (with or without flowing air, or with flowing humid air) were very small on the dispersion of Mo oxide species under the present preparation conditions. On the other hand, the methanol oxidation activity of MoO₃/Al₂O₃ was sensitive to the preparation parameters examined here. It was demonstrated by means of EPMA and XPS that a considerable migration of Mo took place during the calcination.

In the present study on the preparation of a 13 wt% MoO₃/Al₂O₃ catalyst, an impact index is proposed to measure the magnitude of the effects of the respective parameter(s) on the physicochemical and catalytic properties. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support >> drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere. The size of the impact index for the dispersion of Mo sulfide species is 70–75% of that for the Mo oxide species. The HDS activity of the catalyst was less affected by the preparation parameters than the Mo sulfide dispersion. The preparation parameters affected the segregation of Mo on the outer surface of extrudates in a decreasing order: drying process > volume of the impregnation solution > pH, calcination conditions. It was found that the oxidation of methanol was affected most intensely by the drying procedures. The volume of the impregnation solution, calcination conditions and pH of the impregnation solution also strongly affected the oxidation activity. The impact index suggests that the sensitivity to the preparation variables of the physicochemical and catalytic properties of MoO₃/Al₂O₃ decreases in the order, methanol oxidation activity > surface Mo segregation > Mo oxide dispersion > Mo sulfide dispersion > HDS activity.     

Fault-surge calculation using phase-domain ARMA line model

For fault-surge studies, the most important and also most difficult part of the simulation is inclusion of the frequency dependence of the transmission line, because the simulation requires high accuracy in a wide frequency range, from the power frequency to a few megahertz. The authors have developed a highly efficient method of modeling a transmission line considering its complete frequency dependence, which cannot be dealt with in the present line models in the Electro-Magnetic Transients Program (EMTP). According to the method, a transmission line is modeled directly in the phase domain in order to avoid model transformation and thus to eliminate the problems of representing its frequency dependence. The method also includes sophisticated acceleration of transient calculations by means of an autoregressive moving average (ARMA) model. This paper presents a method of steady-state initialization of the phase-domain ARMA line model for applying it to fault-surge calculations. The calculated results agree well with rigorous frequency-domain simulations and show improved accuracy compared with an existing frequency-dependent line model (J. Marti model) widely used as a standard model in the EMTP. © 1998 Scripta Technica, Inc. Electr Eng Jpn, 121(3): 27–35, 1997     

Transmission capacity of longitudinal power systems and SVC voltage control

Power transfer between systems is important due to uneven distribution of generating plants. This paper investigates the relation between the transfer capacity of a longitudinal power system and voltage control of static var compensators. The transfer capacity is basically limited by the thermal capacity of transmission lines. However, the practical systems, it is much restricted by stability and the power transfer level is considerably lower than the thermal capacity. In this paper, we consider a basic case in which SVCs are applied to all buses except generator terminals. In this case, it is possible to transfer power up to the reciprocal of the transmission reactance. Two modifications are then applied to the basic case. One is removal of SVCs on the high-voltage sides of the generator transformers. In this case, generator damping torques deteriorate, and the local oscillation mode becomes unstable. The other is removal of SVCs at intermediate buses on the trunk system. In this case, the shapes of the oscillation modes change greatly, and the global mode becomes unstable. The voltage control of SVCs maintains the generator damping torques and prevents deformation of mode shapes. By investigating different system sizes and transmission circuits, we show that the system transfer capacity is determined by the capacities of the individual transmission lines. © 1997 Scripta Technica, Inc. Electr Eng Jpn, 119(3): 49–60, 1997