Incompatibility between Propericiazine Oral Solution and Tea-Based Drink

Here, we studied the incompatibility between an oral solution of propericiazine (PCZ), an antipsychotic drug, and various commercially available bottled tea-based drinks. When 0.5?mL of the PCZ oral solution (10?mg/mL) was mixed with 16.5?mL of a tea-based drink (such as green tea, oolong tea, and black tea), the residual PCZ content declined to approximately 50% in some mixed solutions. After mixing with other tea-based drinks, the residual PCZ content declined to approximately 30%, while in others, it changed very little. The residual PCZ content declined immediately after mixing with tea-based drinks, but the rate remained almost unchanged for the next 24?h. Furthermore, the pH of the mixture increased to 4.5-5.1 after the oral solution of PCZ (original pH 3.8) was diluted with various tea-based drinks. Afterwards, the pH did not change for 24?h. The mixture became cloudy immediately after diluting PCZ oral solution with tea-based drinks, and the insoluble substance gradually precipitated. In order to elucidate factors responsible for the decline in the content of PCZ, a (-)-epigallocatechin gallate solution, which is a main ingredient of green tea polyphenol, was mixed with the PCZ oral solution. After mixing, the residual PCZ content declined to approximately 60-75%. On the other hand, the content of PCZ did not decline when a (-)-epigallocatechin solution was mixed with the PCZ oral solution. The results from this study demonstrated that PCZ content was reduced after dilution in tea-based drinks because of the interaction between PCZ and polyphenol with a galloyl group in tea-based drinks.     

Liquid phase behavior of ionic liquids with alcohols: experimental studies and modeling

Ionic liquids (ILs) have been suggested as potential "green" solvents to replace volatile organic solvents in reaction and separation processes due to their negligible vapor pressure. To develop ILs for these applications, it is important to gain a fundamental understanding of the factors that control the phase behavior of ionic liquids with other liquids. In this work, we continue our study of the effect of chemical and structural factors on the phase behavior of ionic liquids with alcohols, focusing on pyridinium ILs for comparison to imidazolium ILs from our previous studies. The impact of different alcohol and IL characteristics, including alcohol chain length, cation alkyl chain length, anion, different substituent groups on the pyridinium cation, and type of cation (pyridinium vs imidazolium) will be discussed. In general, the same type of behavior is observed for pyridinium and imidazolium ILs, with all systems studied exhibiting upper critical solution temperature behavior. The impacts of alcohol chain length, cation chain length, and anion, are the same for pyridinium ILs as those observed previously for imidazolium ILs. However, the effect of cation type on the phase behavior is dependent on the strength of the cation-anion interaction. Additionally, all systems from this study and our previous work for imidazolium ILs were modeled using the nonrandom two-liquid (NRTL) equation using two different approaches for determining the adjustable parameters. For all systems, the NRTL equation with binary interaction parameters with a linear temperature dependence provided a good fit of the experimental data.     

Palladium-catalyzed aerobic intermolecular cyclization of acrylic acid with 1-octene to afford α-methylene-γ-butyrolactones: the remarkable effect of continuous water removal from the reaction mixture and analysis of the reaction by kinetic, ESI-MS, and XAFS measurements

Further study of our aerobic intermolecular cyclization of acrylic acid with 1-octene to afford α-methylene-γ-butyrolactones, catalyzed by the Pd(OCOCF(3))(2)/Cu(OAc)(2)?H(2)O system, has clarified that the accumulation of water generated from oxygen during the reaction causes deactivation of the Cu cocatalyst. This prevents regeneration of the active Pd catalyst and, thus, has a harmful influence on the progress of the cyclization. As a result, both the substrate conversion and product yield are efficiently improved by continuous removal of water from the reaction mixture. Detailed analysis of the kinetic and spectroscopic measurements performed under the condition of continuous water removal demonstrates that the cyclization proceeds in four steps: 1)?equilibrium coordination of 1-octene to the Pd acrylate species, 2)?Markovnikov-type acryloxy palladation of 1-octene (1,2-addition), 3)?intramolecular carbopalladation, and 4)?β-hydride elimination. Byproduct 2-acryloxy-1-octene is formed by β-hydride elimination after step 2). These cyclization steps fit the Michaelis-Menten equation well and β-hydride elimination is considered to be a rate-limiting step in the formation of the products. Spectroscopic data agree sufficiently with the existence of the intermediates bearing acrylate (Pd-O bond), η(3)-C(8)H(15) (Pd-C bond), or C(11)H(19)O(2) (Pd-C bond) moieties on the Pd center as the resting-state compounds. Furthermore, not only Cu(II), but also Cu(I), species are observed during the reaction time of 2-8?h when the reaction proceeds efficiently. This result suggests that the Cu(II) species is partially reduced to the Cu(I) species when the active Pd catalytic species are regenerated.     

Chiral η6‐Arene/N‐Tosylethylenediamine–Ruthenium(II) Complexes: Solution Behavior and Catalytic Activity for Asymmetric Hydrogenation

Aromatic ketones are enantioseletively hydrogenated in alcohols containing [RuX{(S,S)‐Tsdpen}(η⁶‐p‐cymene)] (Tsdpen=TsNCH(C₆H₅)CH(C₆H₅)NH₂; X=TfO, Cl) as precatalysts. The corresponding Ru hydride (X=H) acts as a reducing species. The solution structures and complete spectral assignment of these complexes have been determined using 2D NMR (¹H‐¹H DQF‐COSY, ¹H‐¹³C HMQC, ¹H‐¹⁵N HSQC, and ¹H‐¹⁹F HOESY). Depending on the nature of the solvents and conditions, the precatalysts exist as a covalently bound complex, tight ion pair of [Ru⁺(Tsdpen)(cymene)] and X^?, solvent‐separated ion pair, or discrete free ions. Solvent effects on the NH₂ chemical shifts of the Ru complexes and the hydrodynamic radius and volume of the Ru⁺ and TfO^? ions elucidate the process of precatalyst activation for hydrogenation. Most notably, the Ru triflate possessing a high ionizability, substantiated by cyclic voltammetry, exists in alcoholic solvents largely as a solvent‐separated ion pair and/or free ions. Accordingly, its diffusion‐derived data in CD₃OD reflect the independent motion of [Ru⁺(Tsdpen)(cymene)] and TfO^?. In CDCl₃, the complex largely retains the covalent structure showing similar diffusion data for the cation and anion. The Ru triflate and chloride show similar but distinct solution behavior in various solvents. Conductivity measurements and catalytic behavior demonstrate that both complexes ionize in CH₃OH to generate a common [Ru⁺(Tsdpen)(cymene)] and X^?, although the extent is significantly greater for X=TfO^?. The activation of [RuX(Tsdpen)(cymene)] during catalytic hydrogenation in alcoholic solvent occurs by simple ionization to generate [Ru⁺(Tsdpen)(cymene)]. The catalytic activity is thus significantly influenced by the reaction conditions.     

Carbohydrate recognition of symmetrical tripodal receptor type tris(2-aminoethyl)amine derivatives

Carbohydrate recognition of some bioactive symmetrical tripodal receptor type tris(2-aminoethyl)amine (TAEA) derivatives was investigated. In calorimetric experiments, the highest binding constant (Ka) of compound C (C₃₅H₄₉N₅O₄S) with methyl α-d-mannopyranoside was Ka = 858 M^?1 with 1:1 stoichiometry. Formation of hydrogen bonds in binding between symmetrical tripodal receptor type compound C and sugars was suggested by the large negative values of ?H° (=?34 to ?511 kJ mol^?1). In a comparison of each set of α- and β-anomers of some monosaccharides (methyl α/β-d-galactopyranoside, methyl α/β-d-glucopyranoside, and methyl α/β-l-fucopyranoside), compound C showed that the binding constant of β-anomer was larger than that of the corresponding α-anomer, indicating higher β-anomer selectivity. The calculated energy-minimized structure of the complex of compound C with guest methyl α-d-mannopyranoside is also presented. The experimental results obtained from this work indicated that symmetrical tripodal receptor type TAEA derivative C has a lectin-like carbohydrate recognition property.     

Absorption-based highly sensitive and reproducible biochemical oxygen demand measurement method for seawater using salt-tolerant yeast Saccharomyces cerevisiae ARIF KD-003

Salt-tolerant yeast Saccharomyces cerevisiae ARIF KD-003 was applied to highly sensitive and reproducible absorbance-based biochemical oxygen demand (BOD_AB-ScII) measurement for seawater. In the previous work, we have studied the BOD_AB-ScI method using normal Baker's yeast S. cerevisiae, and the excellent feature of the Baker's yeast as uniformly sustainable in solution could successfully be utilized. However, the BOD_AB-ScI responses were disappeared by the existence of chloride ion as well as seawater. In the present method, uniformity in solution was also observed with S. cerevisiae ARIF KD-003, and salt-tolerance of the yeast was observed even in saturate concentration of sodium chloride. Next, characterizations of the influences of pH and incubation temperature were investigated. After optimum conditions were obtained, two calibration curves were made between 0.33 and 22 mg O₂ L⁻¹ BOD using standard solution of glucose glutamic acid (GGA) or mixture of GGA and artificial seawater. Then, excellent reproducibility as the averages of relative standard deviation (R.S.D._av) in two calibration curves (nine points each) was successfully obtained at 1.10% at pure water or 1.03% at artificial seawater standard, respectively. In addition, the 3σ lower detection limit was calculated to be 0.07 mg O₂ L⁻¹ BOD, and 0.11 mg O₂ L⁻¹ BOD was experimentally detected by increase of the sample volume at 1.5-folds. The storage stability of the S. cerevisiae ARIF KD-003 was obtained at least 4 weeks.     

Synthesis of Murisolin, (15R, 16R, 19R, 20S)‐Murisolin A,and (15R, 16R, 19S, 20S)‐16,19‐cis‐Murisolin and Their Inhibitory Action with Bovine Heart Mitochondrial Complex I

The asymmetric total synthesis of murisolin, (15R, 16R, 19R, 20S)‐murisolin A, and (15R, 16R, 19S, 20S)‐16,19‐cis‐murisolin was performed by using an epoxy alcohol as a versatile chiral building block for synthesizing the stereoisomers of mono‐THF annonaceous acetogenins. The inhibitory activity of these murisolin compounds was examined with bovine heart mitochondrial complex I, and they showed almost the same activity.     

Total Synthesis of Pectenotoxin‐2

Pectenotoxin‐2 (PTX2) is a shellfish toxin and has a non‐anomeric spiroacetal, which is not stabilized by an anomeric effect. The selective construction of the non‐anomeric spiroacetal has been a major problem in the synthesis of PTX2. Described herein is the stereoselective total synthesis of PTX2 via the isomerization of anomeric spiroacetal pectenotoxin‐2b (PTX2b). The synthesis of PTX2b was achieved by a simple process including sulfone‐mediated assembly of spirocyclic and bicyclic acetals and subsequent macrocyclization by ring‐closing olefin metathesis. Finally, the selective construction of PTX2 was accomplished by the early termination of a dynamic transition process to equilibrium in the acid‐catalyzed isomerization of anomeric PTX2b. [6,6]‐Spiroacetal pectenotoxin‐2c (PTX2c) was also synthesized from PTX2b. The cytotoxicity assay of the synthetic compounds against HepG2 and Caco2 cancer cells showed a potency of the order: PTX2?PTX2b>PTX2c.     

Anion receptor functions of lanthanide tris(beta-diketonate) complexes: naked eye detection and ion-selective electrode determination of Cl- anion

Lanthanide tris(fluorinated beta-diketonates) acted as effective receptors of Cl- anion in luminescence sensing and ion-selective electrode systems via highly coordinated complexation.