Synthesis and properties of ortho‐linked aromatic polyimides based on 1,2‐bis(4‐aminophenoxy)‐4‐tert‐butylbenzene

A bis(ether amine) containing the ortho‐substituted phenylene unit and pendant tert‐butyl group, 1,2‐bis(4‐aminophenoxy)‐4‐tert‐butylbenzene, was synthesized and used as a monomer to prepare polyimides with six commercial dianhydrides via a conventional two‐stage procedure. The intermediate poly(amic acid)s had inherent viscosities of 0.78–1.44 dL/g, and most of them could be thermally converted into transparent, flexible, and tough polyimide films. The inherent viscosities of the resulting polyimides were in the range of 0.46–0.87 dL/g. All polyimides were noncrystalline, and most of them showed excellent solubility in polar organic solvents. The glass‐transition temperatures of these polyimides were in the range of 222–259 °C in differential scanning calorimetry and 212–282 °C in thermomechanicl analysis. These polyimides showed no appreciable decomposition up to 500 °C in thermogravimetric analysis in air or nitrogen. A comparative study of the properties with the corresponding polyimides without pendant tert‐butyl groups derived from 1,2‐bis(4‐aminophenoxy)benzene is also presented. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1551–1559, 2000     

Syntheses and properties of organosoluble polyimides based on 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐4, 7‐methanohexahydroindan

A series of organosoluble aromatic polyimides (PIs) was synthesized from 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐4,7‐methanohexahydroindan (3) and commercial available aromatic dianhydrides such as 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride (ODPA), 4,4′‐sulfonyl diphthalic anhydride (SDPA), or 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropanic dianhydride (6FDA). PIs (III_c–f), which were synthesized by direct polymerization in m‐cresol, had inherent viscosities of 0.83–1.05 dL/g. These polymers could easily be dissolved in N,N′‐dimethylacetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylformamide (DMF), pyridine, m‐cresol, and dichloromethane. Whereas copolymerization was proceeded with equivalent molar ratios of pyromellitic dianhydride (PMDA)/6FDA, 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA)/6FDA, or BTDA/SDPA, or ½ for PMDA/SDPA, copolyimides (co‐PIs), derived from 3 and mixed dianhydrides, were soluble in NMP. All the soluble PIs could form transparent, flexible, and tough films, and they showed amorphous characteristics. These films had tensile strengths of 88–111 MPa, elongations at break of 5–10% and initial moduli of 2.01–2.67 GPa. The glass transition temperatures of these polymers were in the range of 252–311°C. Except for III_e, the 10% weight loss temperatures (T_d) of PIs were above 500°C, and the amount of carbonized residues of the PIs at 800°C in nitrogen atmosphere were above 50%. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1681–1691, 1999     

Computation of three‐dimensional flow around square and circular piers

The aim of the present study is to investigate, by numerical simulation, the three‐dimensional turbulent flow field around square and circular piers. The numerical model employs a finite volume method based on MacCormack's explicit predictor–corrector scheme to solve weakly compressible hydrodynamic equations for turbulent flow. Computed results are compared with Dargahi's experimental measurements to assess the validity of the proposed model. Very good agreements are obtained. The results of flow simulation indicate that near the upstream face of the pier there exists a downflow, which joins the separated flow to form the horseshoe vortex stretched around the pier. This horseshoe vortex interacts with the wake vortex to create the upflow behind the pier. These phenomena appear to be very important to the mechanism of scouring around the pier. In general, the flow patterns for the square and circular piers are similar. However, the strengths of the downflow and horseshoe vortex are greater in the case of the square pier. The position of the horseshoe vortex around the circular pier is closer to the front face than that around the square pier. In the meantime, the domain of the wake flow in the case of the square pier is greater than that in the case of the circular one. Copyright © 2000 John Wiley & Sons, Ltd.     

Furylhydroquinones and miscellaneous compounds from the roots of Lithospermum erythrorhizon and their anti-inflammatory effect in HaCaT cells

One new furylhydroquinone derivative (1) and seven known compounds (2–8) were isolated from the roots of Lithospermum erythrorhizon Sieb. et Zucc (Boraginaceae). The structure of 1 was elucidated by extensive spectroscopic methods using NMR and MS. The absolute configuration of shikonofuran J (1) was unambiguously determined by aid of comparison experimental ECD with predicted ECD spectra. All the isolates were tested for their inhibitory activities against IL-6 production in HaCaT cells stimulated by tumor necrosis factor (TNF)-α. It was found that gracicleistanthoside (5) and uridine (7) remarkably down-regulated the TNF-α-induced synthesis of interleukin-6 (IL-6), a pro-inflammatory cytokine associated with cutaneous inflammation, in HaCaT cells.     

The formation of dinuclear trichloro-bridged and mononuclear ruthenium complexes from the reactions of dichlorotris(p-tolylphosphine)ruthenium(II) with diazabutadiene ligands

Transition Metal Chemistry - Ru(II) complexes with diazabutadiene (R-DAB) ligands have been prepared. The reaction of RuCl3·nH2O with P(p-tolyl)3 gave a [RuCl2{P(p-tolyl)3}] precursor, whose...     

Binding Sites,Vibrations and Spin-Lattice Relaxation Times in Europium(II)-Based Metallofullerene Spin Qubits

To design molecular spin qubits with enhanced quantum coherence, a control of the coupling between the local vibrations and the spin states is crucial, which could be realized in principle by engineering molecular structures via coordination chemistry. To this end, understanding the underlying structural factors that govern the spin relaxation is a central topic. Here, we report the investigation of the spin dynamics in a series of chemically designed europium(II)-based endohedral metallofullerenes (EMFs). By introducing a unique structural difference, i. e. metal-cage binding site, while keeping other molecular parameters constant between different complexes, these manifest the key role of the three low-energy metal-displacing vibrations in mediating the spin-lattice relaxation times (T₁). The temperature dependence of T₁ can thus be normalized by the frequencies of these low energy vibrations to show an unprecedentedly universal behavior for EMFs in frozen CS₂ solution. Our theoretical analysis indicates that this structural difference determines not only the vibrational rigidity but also spin-vibration coupling in these EMF-based qubit candidates.     

Acoustic Properties of Micro-Perforated Panels Made from Oil Palm Empty Fruit Bunch Fiber Reinforced Polylactic Acid

This paper presents the development and performance of micro-perforated panels (MPP) from natural fiber reinforced composites. The MPP is made of Polylactic Acid (PLA) reinforced with Oil Palm Empty Fruit Bunch Fiber (OPEFBF). The investigation was made by varying the fiber density, air gap, and perforation ratio to observe the effect on the Sound Absorption Coefficient (SAC) through the experiment in an impedance tube. It is found that the peak level of SAC is not affected, but the peak frequency shifts to lower frequency when the fiber density is increased. This phenomenon might be due to the presence of porosity in the inner wall of the holes. Increasing or decreasing the air gap and perforation ratio shifts the peaks of acoustic absorption either way.     

Determination of Penicillium griseofulvum‐oriented pyripyropene A,a selective inhibitor of acyl‐coenzyme A:cholesterol acyltransferase 2, in mouse plasma using liquid chromatography–tandem mass spectrometry and its application to pharmacokinetic studies

In this study, we developed a method for the determination of Penicillium griseofulvum‐oriented pyripyropene A (PPPA), a selective inhibitor of acyl‐coenzyme A:cholesterol acyltransferase 2, in mouse and human plasma and validated it using liquid chromatography–tandem mass spectrometry. Pyripyropene A (PPPA) and an internal standard, carbamazepine, were separated using a Xterra MS C18 column with a mixture of acetonitrile and 0.1% formic acid as the mobile phase. The ion transitions monitored in positive‐ion mode [M + H]⁺ of multiple‐reaction monitoring (MRM) were m/z 148.0 from m/z 584.0 for PPPA and m/z 194.0 from m/z 237.0 for the internal standard. The detector response was specific and linear for PPPA at concentrations within the range from 1 to 5,000 ng/mL. The intra?/inter‐day precision and accuracy of the method was acceptable by the criteria for assay validation. The matrix effects of PPPA ranged from 97.6 to 104.2% and from 93.3 to 105.3% in post‐preparative mouse and human plasma samples, respectively. PPPA was also stable under various processing and/or handling conditions. Finally, PPPA concentrations in the mouse plasma samples could be measured after intravenous, intraperitoneal, or oral administration of PPPA, suggesting that the assay is useful for pharmacokinetic studies on mice and applicable to human studies.