Photochromism of bis(2-alkyl-1-benzofuran-3-yl)perfluorocyclopentene derivatives

[reaction: see text] Photochromic diarylethene derivatives having benzofuran heteroaryl groups, bis(2-methyl-1-benzofuran-3-yl)perfluorocyclopentene and bis(2-butyl-1-benzofuran-3-yl)perfluorocyclopentene, were synthesized, and their photochromic performance was examined in hexane solution as well as in the single-crystalline phase. The compounds exhibited photochromic reactivity even in the single-crystalline phase.     

Franck-Condon factors in the long-range hole transfer in irradiated s-BuCl at 77 K

Franck-Condon factors in the transfer of trapped holes to various solutes were estimated through steady gamma radiolysis at 77 K. These factors increased monotonically over the free energy range up to ?4 eV, indicating a contribution of high-frequency skeleton or CH vibrations and large displacements of the harmonic potential in the transition.     

A new one-electron model for extended Hückel type molecular orbital calculations

A new form of Coulomb and resonance integrals for extended Hückel type molecular orbital calculations was derived. In this model an electron moving in a molecule, when it stays in the neighborhood of the center of an atom in the molecule, sees the potential of the corresponding isolated atom. Compared with the well-known forms of Coulomb and resonance integrals, each integral derived from this model considers the influences from all atoms in the molecule, and includes the concept of atomic cell. The similarities of this model to other extended Hückel type formulations are also examined.     

Über die Einkristalle von Polyparaxylylen

Zusammenfassung Aus verdünnter L?sung kristallisiert Polyparaxylylen in zweierlei Form, als rechteckige und als hexagonale Einkristalle, die sich in ihren Elektronenbeugungs- und in ihren R?ntgenbildern voneinander unterscheiden. Durch die r?ntgenographischen Messungen wurde festgestellt, da? diese zweierlei Einkristalle dem α- und dem β-Kristall entsprechen, die bereits beim massiven Material beobachtet werden. Die Kristallisations-bedingungen, die die morphologischen Strukturen der hergestellten Einkristalle sehr stark beeinflussen, wurden untersucht. Tempereffekte sowie dabei stattfindende Umwandlung von α- zu β-Form durch R?ntgen- und DTA-Messungen verfolgt.

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Summary Poly-p-xylylene crystallizes from some solvents into two single crystal forms, rectangular and hexagonal. These two single crystals show different X-ray and electron diffraction patterns, respectively. By X-ray measurements it was found that these two single crystals correspond to α- und β-crystal forms, which were observed with bulk materials by Brown and Farthing. It was also found that these morphological forms depend on the crystallization-conditions, especially on crystallization-solvents. The annealing effects and the transformation from α- to β-form were studied by X-ray diffraction and differential thermal analysis.

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Vorgetragen auf dem International Symposium on Makromolecular Chemistry, Kyoto, 3. Okt. 1966.

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Herrn Professor Dr. E. W. Fischer danken die Autoren für viele f?rdernde Diskussionen.     

Study of solvated electrons in ethanol−Water mixtures at 77 K

Solvated electrons in ethanol-water mixtures at 77 K were investigated by optical absorption and ESR measurements over a wide range of concentrations. Abrupt changes of yield and spectral parameters were observed betwenn 12 and 14 mol% ethanol where a structural transition of the mixture had been reported.     

Photochromism of dinaphthylethene derivatives. Stability of the closed-ring forms

Stability of various types of closed-ring forms of dinaphthylperfluorocyclopentenes was investigated from both experimental as well as theoretical points of view. The stability was dependent on the energy differences between the open-ring and the closed-ring forms. When the energy difference was small, the closed-ring form became stabler.     

Radiation-induced solid-state polymerization of methacrylic acid. III. Post-polymerization

The post-polymerization of methacrylic acid in the solid state was studied. The decay of the trapped radicals was also observed by ESR measurements. The decay of trapped radicals is a first-order reaction below 0°C but a second-order reaction at + 10°C. The results of the post-polymerization were compared with the results of radical decay measurements. A kinetic scheme was proposed for the post-polymerization of methacrylic acid. The effect of conditions of monomer crystallization on the polymer yield was also investigated. Fine crystals gave a greater limiting conversion than large crystals. The addition of water to the monomer increased the polymer yield. The change in the ESR spectrum during post-polymerization was interpreted in terms of the change in the matrix which surrounds the propagating radicals.     

Utility of 2-hydroxypropyl-beta-cyclodextrin in an intramuscular injectable preparation of nimodipine

Possible utility of hydroxyalkylated beta-cyclodextrin (beta-CyD) derivatives as parenteral drug carriers was investigated, using nimodipine, a dihydropyridine derivative with calcium antagonistic action, as a model drug. The aqueous solubility of nimodipine increased linearly with increase in the concentration of hydroxyalkylated beta-CyDs, showing an AL-type phase solubility diagram. The stability constant of nimodipine--hydroxyalkylated beta-CyD complexes was in the order of 2,3-dihydroxypropyl-beta-CyD less than beta-CyD less than 2-hydroxyethyl-beta-CyD less than 3-hydroxypropyl-beta-CyD less than 2-hydroxypropyl-beta-CyD, and the solubilizing ability of the beta-CyDs was also in that order. The results of powder X-ray diffractometry and thermal analysis suggested 1:3 (guest:host) complex formation of nimodipine with 2-hydroxypropyl-beta-CyD in the solid state. The dissolution rate of nimodipine-2-hydroxypropyl-beta-CyD complex was much faster than that of the drug alone. Nimodipine-2-hydroxypropyl-beta-CyD complex gave higher plasma levels of the drug after intramuscular administration to rabbits, i.e., the area under the plasma concentration--time curve and the maximum plasma concentration of the complex were about 2.5 times higher than those of the drug alone. The muscular damage after the injection of nimodipine was reduced by the administration of the complexed form.     

Radiation-induced solid-state polymerization of methacrylic acid. II. In-source polymerization

The in-source polymerization of methacrylic acid in the solid state with γ-rays was studied. The conversion rates at various temperatures were obtained as well as the radical concentrations by the measurements of ESR spectrum. The rate of polymerization was found to be proportional to I^0.65 at 0°C. The results could be interpreted on the basis of the assumption that the rate of propagation is proportional to the concentration of the propagating radical, of the monomer, and of the polymer. The addition of water to the monomer seems to accelerate the polymerization reaction. The change of the line shape of the propagating radical during polymerization was interpreted in terms of the change of the matrix which surrounds the propagating radical.     

Synthesis of 23,23-difluoro-25-hydroxyvitamin D3

23,23-Difluoro-25-hydroxyvitamin D₃ was synthesized from 6β-methoxy-3α,5-cyclo-23,24-dinor-5α-cholan-22-ol.