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  • Organic Chemistry  (2,261)
  • Occupational Health and Environmental Toxicology  (147)
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  • Wiley-Blackwell  (2,408)
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  • 1
    ISSN: 0197-8462
    Keywords: millimeter-wave radiation ; BHK-21/C13 cells in monolayer culture ; scanning electron microscopy ; transmission electron microscopy ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Both thermal and athermal effects of millimeter-wave radiation on BHK-21/C13 cells were sought using scanning and transmission electron microscopy in conjunction with an in vitro technique that allows direct exposure of monolayer cultures to high average power densities. Culture dishes were irradiated by placing them on the open end of an E- or U-band wave guide. This technique exposes different regions of the cell monolayer lying along the longer axis of the wave guide aperture to varying power densities ranging from zero at each edge to twice the average power density at the center.Cell ultrastructure was unaffected by microwave radiation for 1 hour (41.8 or 74.0 GHz, average power densitites = 320 or 450 mW/cm2, respectively) with or without cooling by rapid recirculation of the culture medium. Temperature in recirculated cultures was held at 37.2 °C, and that in noncooled cultures never exceeded 42 °C during irradiation at either power density. In contrast, cell morphology was affected by microwave exposure whenever irradiation conditions were altered so that the temperature of the monolayer reached or exceeded 44.5 °C. Ultrastructural alterations included breakage of cell processes, progressive detachment of cells from the substrate, increased clumping of heterochromatin in the nuclei, and the appearance of large empty vesicles in the cytoplasm. Such morphological changes resulted from either application of higher average power densities or irradiation at the power densities described above at a higher ambient temperature (〉38.5°C).
    Additional Material: 5 Ill.
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  • 2
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: α-Aminoadipoyl-alanyl-valine, α-aminoadipoyl-serinyl-valine and α-aminoadipoyl-serinyl-isodehydrovaline have been isolated from the fermentation broth of P. chrysogenum. The configuration of α-aminoadipoyl-serinyl-valine has been shown to be L, L, D.
    Additional Material: 11 Ill.
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  • 3
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eine thermische (a) und eine reduktive (b) Methode zur Herstellung von Mikanez-Estern wird beschrieben. Bei der ersten gelang der Nachweis des monomeren Vorläufers, 1,3-Butadien-2-carboxylester. (a)trans/cis-Gemische von Methyl resp. Äthyl 2-Brom-1-methylcyclopropancarboxylat (14/15 resp. 16/17), mit Tri-n-butylzinnhydrid aus den entsprechenden 2,2-Dibrom-1-methylcyclopropancarboxylaten 12 resp. 13 hergestellt, wurden bei 480°/1,7 Torr pyrolysiert. Die bei -78° daraus abgefangenen Kondensate bestanden aus den 1,3-Butadien-2-carboxylaten 5 und 6, im Falle des Äthylesters 6 durch seine 1H-NMR.-Signale charakterisiert und als Addukt (19) mit 4-Phenyl-1,2,4-triazolin-3,5-dion (18) abgefangen (55%). Beim Erwärmen der Kondensate dimerisierten die Dienester 5 resp. 6, so dass sich Dimethyl resp. Diäthyl Mikanezat (9 resp. 10) isolieren liess (67 resp. 100%).(b)Behandlung von Methyl 2(E)-2-Methyl-2-butenoat (20) mit 2 Äquivalenten N-Bromsuccinimid gab (25%) Methyl 2(Z)-4-Brom-2-brommethyl-2-butenoat (21). (Mit 3 Äquivalenten entstand ein Stereomerengemisch 2(Z)- und 2(E)-4,4-Dibrom-2-brommethyl-2-butenoat (22 und 23)). Reduktion des Dibromesters 21 mit Zink in Tetrahydrofuran, Methanol oder Eisessig ergab (50%) Dimethyl Mikanezat (9). Von einer Iodolaktonisierung der aus 9 durch Verseifung hergestellten Mikanezsäure (8) erhielt man 4-Iodo-7-oxo-1-vinyl-6-oxabicyclo[3.2.1]octan-4endo-carbonsäure (24), dessen Bildungsleichtigkeit und IR.-Bande bei 1780 cm eine unabhängige Bestätigung dafür liefert, dass Mikanezsäure (8) durch Kopf-zu-Kopf-Diels-Alder-Dimerisierung von 1,3-Butadien-2-carbonsäure (4) entsteht.Aus Methyl (E)-2-Methyl-2-pentenoat (25) wurde auf gleiche Weise, d.h. über Dibromierung zu 27 und Reduktion mit Zink in Äther, Dimethyl 3,2′-Dimethylmikanezat (29) gewonnen. Die Multiplizität des 1H-NMR.-Signals von H—C(3) in 29 bestätigt, wiederum unabhängig, dass die Dimerisierung des Dienesters (in diesem Fall 28) in Kopf-zu-Kopf-Diels-Alder-Weise stattfindet.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 25 (1942), S. 621-630 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 5
    ISSN: 0197-8462
    Keywords: millimeter-wave radiation ; BHK-21/C13 cells in monolayer culture ; quantitative autoradiography ; ribonucleic acid (RNA) synthesis ; protein synthesis ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: A method has been devised whereby both the thermal and possible athermal biological effects resulting from microwave radiation can be assessed. Monolayer cultures of BHK-21/C13 cells were grown on microwave-transparent polystyrene coverslips, placed directly on the open end of a wave guide, and irradiated for 1 hour. In experiments seeking athermal biological effects of millimeter waves, culture medium was continuously recirculated over the cells to prevent temperature increases greater than 0.1 °C. Incorporation of 3H-uridine into RNA and of 3H-methionine into protein was quantified by measurement of optical densities of the autoradiographs in contiguous rectangular regions corresponding to portions of the cell monolayer immediately above the wave guide aperture and lying along its longer axis. Since power density was shown to vary with position along this axis according to a cosine2 relationship, it was possible to assess the extent of microwave effects on macromolecular synthesis at power densities ranging from zero at each edge to twice the average power density at the center of the waveguide.Monolayer cultures maintained at 37.2 °C by recirculation of the medium did not show microwave-induced changes in synthesis of RNA and protein (41.8 or 74.0 GHz at average power densities of 320 or 450 mW/cm2, respectively). Since macromolecular synthesis was examined both during and after irradiation, our results exclude both transient and persistent athermal biological effects of acute exposure to millimeter waves. In contrast, irradiation of cultures incubated in a small volume of nonrecirculated medium resulted in 1) marked heating of the monolayer, 2) a graded decline in macromolecular synthesis with increasing incident power, and 3), in some cases, destruction of the cell monolayer in the region immediately above the center of the waveguide aperture.
    Additional Material: 12 Ill.
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  • 6
    ISSN: 0197-8462
    Keywords: protein synthesis ; quantitative autoradiography ; BHK-21/C13 cells ; millimeter-wave radiation ; frequency-specific biological effects ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: A method recently developed in this laboratory has been used to directly expose BHK-21/C13 cells to high levels of microwave radiation without significant microwave-induced heating (≤ 0.1 °C). Monolayer cultures were grown on microwave-transparent polystyrene coverslips, placed on the open end of a wave guide, and maintained at 37.2 °C during irradiation at frequencies in both the E- and U-bands (average power densities 292 and 177 mW/cm2, respectively). Effects of microwave radiation were assessed at 0.1 GHz increments in the ranges of 38-48 GHz and 65-75 GHz. Protein synthesis was measured in quadruplicate cultures that were allowed to incorporate labeled methionine during the 15-minute period of microwave irradiation. Autoradiographs of each monolayer culture were scanned along the region corresponding to the longer axis of the wave guide aperture using a microdensitometer to quantify incorporation. Since microwave power incident on the cells was previously shown to vary along this axis according to a cosine2 relationship from zero at each edge of the wave guide to twice the average power density at the center of the wave guide, this technique should reveal biological effects that might only be manifested in narrow amplitude domains or “power windows.” Observations of protein synthesis in monolayer cultures irradiated at 202 closely spaced frequencies in the E- and U-bands failed to reveal changes associated with microwave exposure. Thus no evidence was obtained in support of the existence of frequency-specific athermal biological effects of microwaves. In addition, no support was found for the existence of amplitude-specific “power windows”.
    Additional Material: 6 Ill.
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  • 7
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pure pencillin N α-sulfoxide (1) and penicillin N β-sulfoxide (2) were obtained by HPLC and tested as substrates for deacetoxycephalosporin C synthetase (DXCS). Neither one of the sulfoxides was utilized under conditions of conversion of penicillin N (8) to deacetoxycephalosporin C (9). The cephalosporin C α and β-sulfoxides (3 and 4, resp.) were also prepared. Relative stabilities of the sulfoxides 3 and 4 are discussed by interpretation of the 13C-NMR spectra.
    Additional Material: 9 Ill.
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  • 8
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two pairs of enantiomerically pure cis-fused cyclopenteno-1,2,4-trioxanes (7, ent-7 and 8, ent-8) are prepared (Schemes 1-3). Their identities are established by dye-sensitized photo-oxygenation of ent-7 and 8, ent-8 to the allylichydroperxides, reduction to the corresponding alcohols, and conversion to the (1S)-camphanates (Scheme 4), the structures of which are determined by X-ray analysis. The dynamic properties of ent-7 are investigated by NMR spectroscopy and PM3 calculations. Evidence for an easily accessible twist-boat conformation is obtained. The in vitro and in vivo antimalarial activities of 7, ent-7,8, and ent-8 as well as those of the racemic mixtures are evaluated against Plasmodium falciparum, P. berghei, and P. yoelii. No correlation is observed between configuration and activity. Racemates and pure enantiomers have commensurate activities. The mode of action on the intraerythrocytic parasite is rationalized in terms of close docking by the twist-boat conformer of the trioxane on the surface of a molecule of heme, single-electron transfer to the O—O σ* orbital, and scission to the acetal radical which then irreversibly isomerizes to a C-centered radical, the ultimate lethal agent (Scheme 5).
    Additional Material: 5 Ill.
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  • 9
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Catharanthus roseus cells suspended in production medium showed the presence of four Aspidosperma-type alkaloids, however, no vindoline. Cells grown in media with the pH adjusted to 7.0 produced 3.3 mg total alkaloids/g dry weight. At pH 5.0, 1.7 mg of alkaloid/g dry weight was produced. (S)-Adenosyl-methionine did not stimulate the production of vindoline. When added to cell suspensions for 21 days, vindoline and catharanthine were degraded to non-alkaloidal substances, not dimerized to bisindole alkaloids.
    Additional Material: 3 Tab.
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  • 10
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cell-free systems from Catharanthus roseus plants are utilized for various studies relating to the biosynthesis of indole alkaloids. Tryptamine (5) and secologanin (6), two fundamental building units, are shown to be incorporated into the alkaloid vindoline (7). In another study, catharanthine (18) and vindoline (7) are utilized by this enzyme system and coupled to the important bisindole biointermediate 3′,4′-anhydrovinblastineThe previously [20] used name for 17, 3′, 4′-dehydrovinblastine, is incorrect. (17). The latter substance is, in turn, incorporated and converted to the natural alkaloids leurosine (8), Catharine (9) and vinblastine (10), thereby providing information about the biosynthesis of these complex molecules. High pressure liquid chromatography assay of the enzymic mixture sheds light on the enzymes involved in the coupling of 18 and 7.
    Additional Material: 5 Ill.
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