Thermal Transformation of Ring-Opened [2 2] C60 Dimer into a Wide-Bridged C120 Isomer. A Computational Evaluation of Fulvalene-Naphthalene Rearrangements

As a continuation of the studies on thermal transformation of the [2+2] C₆₀ dimer (1), the consequence of the pyracylene-rearrangement-like valence isomerization of the fulvalene partial structure at the bridge of the ring-opened product from 1, namely 2, was searched by dynamic reaction coordinate /AM1 semiempirical MO calculations. It is predicted that the fulvalene bridge of 2 rearranges into naphthalene partial structure by the concerted 'in-plane' mechanism to give a wide-bridged C₁₂₀ intermediate having twenty five-membered rings and two ten-membered rings (3). The computed energy of activation (145 kcal/mol) is 40 kcal/mol lower than those computed for pyracylene rearrangements. In contrast, the recently reported analogous rearrangement of indigo (13) to dibenzonaphthyridindione (14) is computed to occur by the stepwise 'sp³' mechanism.     

Studies on calcium antagonistic and alpha 1-adrenergic receptor blocking activities of monatepil maleate, its metabolites and their enantiomers

The calcium antagonistic and alpha 1-adrenergic receptor blocking activities of monatepil maleate (CAS 103377-41-9, (+/-)-N-(6,11-dihydrodibenzo [b, e] thiepin-11-yl) -4-(4-fluorophenyl)-1-piperazinebutanamide monomaleate, AJ-2615), a novel calcium antagonist, its metabolites and their enantiomers were studied in vitro. Monatepil maleate inhibited calcium-induced contractions of rat thoracic aorta (pA2 = 8.71) and l-phenylephrine-induced contractions of rabbit superior mesenteric artery (IC50 = 56.6 nmol/l). The calcium antagonistic activities of the metabolites of monatepil maleate (AJ-2615-sulfoxide A, AJ-2615-sulfoxide B and AJ-2615-sulfone) were 1/10 of that of monatepil maleate. However, their alpha 1-adrenergic receptor blocking activities were similar to or slightly more potent than that of monatepil maleate. The potencies of the calcium antagonistic activities of monatepil maleate and its enantiomers [(S)-AJ-2615 and (R)-AJ-2615] were in the order of (S)-AJ-2615 > monatepil maleate > (R)-AJ-2615 whereas no difference was observed among them in alpha 1-adrenergic receptor blocking activity. In calcium antagonistic and alpha 1-adrenergic receptor blocking activities, there was no difference between the enantiomers of monatepil maleate metabolites. In conclusion, there was a difference with several times in calcium antagonistic activity between the two enantiomers of monatepil maleate but not in their alpha 1-adrenergic receptor blocking activity.     

Novel Constitutive Equation for Predicting Dynamic Recrystallization During Hot Working Considering the Efficiency of Power Dissipation

The efficiency of power dissipation (η) in a dynamic material model has been conventionally used for qualitative predictions to estimate the hot working conditions at which dynamic recrystallization (DRX) is dominant. However, predicting the quantitative value of the DRX fraction (X_DRX) from η remains a challenge. In this paper, a constitutive equation is proposed to quantitatively predict X_DRX using η. The proposed equation for describing X_DRX is derived from the reaction rate equation using the assumption that the DRX rate depends on η. The proposed equation is verified via hot compression tests of equiaxed Ti–6Al–4V ELI alloys (Ti-64) in the (α + β) region. The predicted and experimental X_DRX values are found to be generally consistent with one another, exhibiting an average absolute error of 0.05. Furthermore, the proposed equation provides the same level of prediction accuracy as the conventional Johnson–Mehl–Avrami–Kolmogorov (JMAK) equation. Therefore, the proposed equation can be used to quantitatively predict X_DRX following hot compression tests of equiaxed Ti-64. Moreover, compared with the JMAK equation, the proposed equation is expressed in fewer parameters and constant terms. It is, thus, expected to facilitate the quantitative prediction of X_DRX.

     

The relationship between the molecular weight and the critical miscibility composition of a solvent-nonsolvent-terpolymer system

A theoretical equation for the dependence of the apparent molecular weight measured by light scattering on the solvent used has been derived with regard to the composition heterogeneity. Terpolymers corresponding to a partial azeotrope were synthesized from styrene, acrylonitrile, and methyl methacrylate with mole fractions of 0.55, 0.16, and 0.29, respectively. The molecular weight measured by light scattering was found to be independent of the solvent used. Therefore the terpolymer was concluded to be apparently homogeneous in composition. The relationship between the molecular weight M of the terpolymer and the volume fraction of the nonsolvent γ in the solvent mixture at the precipitation point in a butanone-methanol-terpolymer system was experimentally proved to follow the equation where γ₀ and b′ are constants. Between the molecular weight and the limiting viscosity number [η] of the terpolymer the following relationships are valid at 35°C: and      

A facile chemical synthesis of cholest-4-en-3-one. Carbon-13 nuclear magnetic resonance spectral properties of cholest-4-en-3-one and cholest-5-en-3-one

This paper presents a simplified method for the chemical synthesis of cholest-4-en-3-one, which is a naturally occurring steroid and a salient intermediate in steroid chemistry. Pyridinium chlorochromate (PCC) in refluxing benzene has been found to be an effective and convenient reagent for the oxidation and concomitant isomerization of cholest-5-en-3β-ol (cholesterol) to cholest-4-en-3-one in high yield. Also described are the carbon-13 nuclear magnetic resonance spectral properties of cholest-4-en-3-one and of the isolated reaction intermediate cholest-5-en-3-one. Based on a paper presented at the Symposium on Plant and Fungal Sterols: Biosynthesis Metabolism and function held at the AOCS Annual Meeting, Baltimore, MD, April 1990.     

Larval osmeterial secretions of the swallowtails (Papilio)

The larval osmeterial secretions of sixPapilio species examined displayed a remarkable qualitative change at the fourth larval ecdysis. The secretions of 4th (penultimate) instar larvae ofP. machaon, P. memnon, P. helenus, P. bianor, andP. maackii principally comprised mono- and/or sesquiterpenoids. The compounds identified from these species included -pinene, sabinene, -myrcene, limonene, -phellandrene, (Z)--ocimene, (E)--ocimene, -elemene, -caryophyllene, (E)--farnesene, -selinene, (E,E)--farnesene, germacrene-A, germacrene-B, caryophyllene oxide, methyl 3-hydroxy-n-butyrate, and acetic acid. In contrast, the secretion of 4th larval instar ofP. xuthus, although containing similar terpenic compounds, was accompanied by large amounts of aliphatic acids and their esters: isobutyric acid, 2-methylbutyric acid, methyl isobutyrate and methyl 2-methylbutyrate. On the other hand, the osmeterial secretions of 5th (last) instar larvae varied little in quality among the six species, and the identified compounds consisted of isobutyric acid, 2-methylbutyric acid, methyl isobutyrate, ethyl isobutyrate, methyl 2-methylbutyrate, ethyl 2-methylbutyrate, and isovaleric acid, the last of which was specific toP. bianor andP. maackii. The chemical alteration of osmeterial exudate synchronized at the final larval ecdysis with the larval morphological change (particularly in body coloration) that appears to be of defensive significance against predators.     

Reflection-grating self-pumped phase conjugation with optical feedback free of input conditions

A reflection-grating self-pumped phase-conjugate mirror is demonstrated with a photorefractive KNbO(3) crystal in a novel ring configuration. The feedback beam in the ring configuration is made to track the input probe beam automatically so that the phase conjugation is sustained without readjustment of the optical feedback loop when the angle or the position of the input probe beam is changed. The tracking feedback is realized by means of a simple three-lens erect imaging system. The angular and the positional acceptances for a tightly focused input beam of 50-μm diameter are Δθ(x). = 55 mrad, Δθ(y), = 67 mrad, and Δ(x) = 2.1 mm, Δ(y) = 4.2 mm, respectively.