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  • General Chemistry  (890)
  • Analytical Chemistry and Spectroscopy  (849)
  • Cell & Developmental Biology  (372)
  • Wiley-Blackwell  (2,111)
  • 1980-1984  (2,111)
  • 1970-1974
  • 1980  (2,111)
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  • Wiley-Blackwell  (2,111)
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  • 1980-1984  (2,111)
  • 1970-1974
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Cell Motility and the Cytoskeleton 1 (1980) 
    ISSN: 0886-1544
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
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  • 2
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    Cell Motility and the Cytoskeleton 1 (1980), S. 1-15 
    ISSN: 0886-1544
    Keywords: centrosomes ; kinetochores ; microtubule initiation ; nuclease enzymes ; electron microscopy ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: A lysed cell system was used to study the organelle structure and nucleation of exogenous tubulin at kinetochores and centrosomes in mitotic PtK2 cells. We have used this lysed cell system in conjunction with nuclease digestion experiments to determine which specific nucleic acids (DNA or RNA) are involved in either the structure and/or microtubule-initiating capacity of kinetochores and centrosomes. The results indicate that DNase I specifically decondenses the kinetochore plate structure, with the eventual loss in the ability of the chromosomes to nucleate microtubule assembly. DNase I had no effect on either the structure or nucleating capacity of centrosomes. Both RNase T1 and RNase A specifically attacked the amorphous pericentriolar material of the centrosomes, with a concomitant loss in the ability of this material to nucleate microtubule formation. Neither RNase appeared to affect the structure or nucleating capacity of the kinetochore. Therefore, the two types of nucleases appear to exert preferential effects on the different types of microtubule initiation sites in mitotic mammalian cells. The results suggest that DNA is a major component of the kinetochore, while RNA is a major component of the amorphous pericentriolar material. These findings support the concept that microtubule initiation sites in mitotic cells contain nucleic acids which are essential for the structural and functional integrity of the sites.
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  • 3
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    Cell Motility and the Cytoskeleton 1 (1980), S. 31-40 
    ISSN: 0886-1544
    Keywords: actin ; fascin ; actin cross-linking proteins ; fertilization ; microvilli ; sea urchin eggs ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Following fertilization, the sea urchin egg cortex undergoes a structural change involving the assembly and organization of actin filaments into microvilli. Antifascin localizes this actin cross-linking protein in the microvilli of the fertilized egg cortex but no organized staining is present in the unfertilized cortex. Determination of the actin content of eggs using the DNAase I inhibition assay indicates that actin is about 1.4% of the total protein. Approximately 90% of this actin is soluble in low calcium isotonic extracts of unfertilized eggs while only 60-65% can be recovered in identical extracts of fertilized eggs. Similar measurements for fascin using a radioimmunoassay indicate this molecule represents about 0.3% of the total egg protein, essentially all of which is recovered in low calcium isotonic extracts of unfertilized eggs. After fertilization only 65-70% of this actin cross-linking protein is in the soluble phase. These results demonstrate a markedly different solubility for actin and fascin after fertilization, when the indirect immunofluorescence staining localizes fascin in the microvilli, and are consistent with the idea that fascin organizes newly polymerized actin filaments into the microvillar cores. A consideration of the amounts of actin and fascin incorporated into the cortex after fertilization and the number of microvilli on the egg surface indicates that the measured values are sufficient to account for the observed microvillar elongation.
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  • 4
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    Cell Motility and the Cytoskeleton 1 (1980), S. 17-29 
    ISSN: 0886-1544
    Keywords: Ca-ion ; Labyrinthula ; contraction ; glycerination ; Ca-reservoir ; cell movement ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Colonies of Labyrinthula, a colonial marine protist, expand by protrusive movements of the specialized slimeways. The movements recorded in time-lapse films are of two types - filopodial and lamellipodial - and occur at rates equivalent to those of cell translocation.Evidence is presented that Ca2+ regulates the contraction of the actomyosin system of filaments present in the slimeways of Labyrinthula. In glycerinated models or in colonies exposed to ionophore A23187 contraction is evidenced by the occurrence of periodic contractions of the slimeways, giving them the appearance of strings of beads. Glycerinated slimeways contract on the addition of Ca2+ and ATP while slimeways provided with ionophore A23187 contract on addition of Ca2+ alone. The concentration required is 1.1 × 10-7 M Ca2+ while concentrations of 6.2 × 10-8 or lower were ineffective. Rates of contraction were measured in time-lapse films which provide evidence that contractions and beading occur everywhere in the slimeway system. When beading occurs, the 6-nm filaments transform from an array of parallel single filaments into an interwoven meshwork.We have identified by pyroantimonate-OsO4 fixation, as possible Ca2+ reservoirs, deposits of Ca2+ in bothrosomes - structures through which cell secretions pass into the slimeways. The electron-dense deposits are located at the base of the bothrosome and disappear after incubation with EGTA. We propose that the translocation of cells as well as the movements of slimeways may be regulated by the cells through the local measured liberation of Ca2+ from the bothrosome where it is sequestered.
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  • 5
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    Cell Motility and the Cytoskeleton 1 (1980), S. 41-61 
    ISSN: 0886-1544
    Keywords: mitosis ; mitotic spindle ; kinetochore ; microtubule ; micronucleus ; Tetrahymena ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Mitotic micronuclei were isolated from Tetrahymena thermophila and data on spindle ultrastructure were obtained from serial, transverse sections. Comparison of data from nuclei at meta- and early anaphase with data from nuclei at late anaphase showed that during anaphase, sister kinetochores move from the equator to the spindle poles, but kinetochore translocation occurs without any apparent change in either the number or length of kinetochore microtubules. This unprecedented result is ascribed significance with regard to the mechanism of kinetochore transport since there are only a limited number of ways that result could be achieved. The organization of the peripheral sheath changes during anaphase as evidenced by gaps in the sheath at late anaphase. Numerous kinetochore and non-kinetochore microtubules are located in polar regions of the spindle at late anaphase, whereas those regions contained only peripherally arranged microtubules at earlier stages. Tracking of individual kinetochore microtubules in late anaphase nuclei showed that some of them appeared to become incorporated into the peripheral sheath near the pole. At early and late anaphase, crossbridges connect adjacent microtubules throughout the spindle poleward to the kinetochores, as well as in the interzone.
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  • 6
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    Cell Motility and the Cytoskeleton 1 (1980), S. 63-71 
    ISSN: 0886-1544
    Keywords: Physarum polycephalum ; myosin light chains ; polyacrylamide gel electrophoresis ; calcium ; cytoplasmic streaming ; actomyosin ATPase regulation ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Myosin from the slime mold Physarum polycephalum contains three sizes of polypeptides: a heavy chain and two light chains, LC-1 and LC-2. Using a simple qualitative test for calcium binding by comparing electrophoretic migration of the polypeptides in sodium dodecy1 sulfate (SDS) acrylamide gels in the presence and absence of calcium, we have found that Physarum myosin light chain LC-2 migrates with an apparent molecular weight of 16,900 daltons in the presence of the metal ion chelator ethylene glycol bis (B-aminoethyl ether) N,N′-tetraacetic acid (EGTA). However, if calcium chloride is added to the sample prior to electrophoresis, the apparent molecular weight decreases to 16,100. Lanthanide and cadmium ions, but not magnesium, can substitute for calcium. Because the ionic radii of Ca2+, La3+, and Cd2+ are almost identical, we conclude that Physarum myosin LC-2 possesses a very size-specific binding site for calcium. Physarum myosin LC-1 and the heavy chain give no evidence for binding calcium by this test. Since cytoplasmic streaming in the plasmodium of Physarum requires calcium, our evidence indicates that the calcium-binding property of Physarum myosin LC-2 may be important in regulating the production of force by actomyosin in the ectoplasm. Unexpectedly, the myosin light chain in Physarum capable of binding calcium, LC-2, is the essential light chain, while LC-1 is a member of the regulatory class of myosin light chains [V. T. Nachmias, personal communication]. Until now, essential myosin light chains have not been shown to have high affinity divalent cation binding sites. This means a new version of the myosin-based model for actomyosin regulation by calcium may be required to explain cytoplasmic movement in Physarum, and perhaps in other motile systems involving cytoplasmic myosins as well.
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  • 7
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    Cell Motility and the Cytoskeleton 1 (1980), S. 99-112 
    ISSN: 0886-1544
    Keywords: cell motility ; extracellular matrix ; collagen ; glycosaminogly cans ; collagenase ; hyaluronidase ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The effect of specific components of the extracellular matrix on the motility of tissue cells was studied using organ-cultured aggregates of embryonic fibroblasts. Spherical aggregates of chick embryo heart and skin fibroblasts were fused with [3H]-thymidine-labeled aggregates of the identical cell type. The movement of labeled cells into the unlabeled partner aggregate served as an estimate of cell motility in the cultured tissue-like aggregates. Collagenase treatment decreased the collagen content of heart fibroblast aggregates and increased cell motility; ascorbic acid treatment increased the collagen content of skin fibroblast aggregates and decreased cell motility. Reduction of the glycosaminoglycan content with testicular hyaluronidase had no measurable effect on cell motility in heart fibroblast aggregates.
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  • 8
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    Cell Motility and the Cytoskeleton 1 (1980), S. 73-97 
    ISSN: 0886-1544
    Keywords: nematodes ; muscle structure ; mutants ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: A search for new mutants with altered body-wall muscle cell structure has been undertaken in the nematode C elegans. One-hundred seventeen mutants were isolated after mutagenesis with ethyl methanesulfonate or ultraviolet light, enrichment by a motility-requiring test, and screening by polarized light microscopy; 102 of these mutants were in ten previously established genes, whereas 15 mutants permitted the identification of seven new complementation groups in C elegans. Two of the new genes map on linkage group I (unc-94 and unc-95) and four genes are sex linked (unc-96, unc-97, unc-98, and unc-99). One complementation group (unc-100) could not be mapped because of the special characteristics of its cohort mutants. Representative mutants of the mapped genes were examined by polarized light and electron microscopy. All of the mutants exhibit disruptions of the normal A and I band organization of thick and thin filaments. Several of the mutants produce collections of thin filament-like structures. In one of these cases, HE177 demonstrated collections of somewhat wider, intermediate-sized filaments as well, and the HE195 mutant produces paracrystalline aggregates of thin filaments amidst looser arrangements of similar structures. The mutants in newly identified genes, as well as the new mutants in previously established genetic loci, have promise as tools in the study of myofibrillar assembly and function. Among the 22 complementation groups associated with body-wall structure in C elegans, it is likely that some genes code for regulatory and morphogenetic functions in addition to the well-studied structural, contractile, and calcium-associated proteins in muscle.
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  • 9
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    Cell Motility and the Cytoskeleton 1 (1980), S. 113-129 
    ISSN: 0886-1544
    Keywords: tubulin ; Drosophila ; β-ecdysterne ; differentiating ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Drosophila Kc cells exposed to physiological doses of the moulting hormone, β-ecdysone, elongate, become motile, and subsequently aggregate. This pattern of morphogenesis was found to require the assembly of a microtubular cytoskeleton. Tubulin content was significantly increased in hormone-treated cells when compared to controls, as measured by a 3H-colchicine-binding assay. However, determinations of rates of tubulin synthesis and breakdown revealed no difference between control and hormone-treated cells for either parameter. When tubulin content was assayed by methods that do not depend on colchicine-binding activity, no difference between hormone-treated and control cells was observed. These results are discussed in terms of a model in which β-ecdysone affects the distribution of tubulin in “assembly-active” and “assembly-inactive” pools.
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  • 10
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    Cell Motility and the Cytoskeleton 1 (1980), S. 159-162 
    ISSN: 0886-1544
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
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  • 11
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    Cell Motility and the Cytoskeleton 1 (1980), S. 131-140 
    ISSN: 0886-1544
    Keywords: sea urchin coelomocytes ; motility ; filopodial formation and elongation ; ciné film analysis ; scanning electron microscopy ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Sea urchin coelomocytes were examined during their morphological transformation from petaloid to filopodial forms by scanning electron microscopy and ciné film analysis. Petaloid coelomocytes have a variable morphology but, in general, consist of numerous thin sheets of cytoplasm, the petals, arranged in three dimensions around a central nuclear region. The transition to the filopodial form can occur in either substrate-attached or suspended cells and begins with the formation of several microspikes at the edge of each petal. These become more apparent as the cytoplasm between each microspike/filopodium is retracted centripetally. Concomitantly, the diameter of the flattened cell is increased by as much as twofold as the filopodia actively lengthen at a uniform, average rate of 0.5 μm/minute. The transformation process requires ca 15 minutes and is complete when the cell diameter no longer increases. These filopodia are functionally distinct from the passively produced retraction fibers observed in cultured mammalian cells. The formation of filopodia is biphasic and includes both a cytoplasmic retraction phase and an active extension phase.
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  • 12
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    Cell Motility and the Cytoskeleton 1 (1980), S. 141-157 
    ISSN: 0886-1544
    Keywords: axon guidance ; chemotaxis ; haptotaxis substrate pathways ; development ; pattern biology ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: In multicellular organisms, guidance cues are either diffusible molecules or cellular or extracellular surfaces that are found in reproducible locations and that orient migrating cells and cell processes. The pattern of the guidance cues usually determines the complex in vivo migration routes of motile cells and cell processes. Within organisms, guidance cues are found to be organized in two general patterns: (a) broad gradients - such as diffuse chemotactic gradients; (b) discrete routes (substrate pathways) - such as chemotactic gradients confined to long channels, and such as the axon surface which represents a long specific highway for migrating Schwann cells.
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  • 13
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    Cell Motility and the Cytoskeleton 1 (1980), S. 163-163 
    ISSN: 0886-1544
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 14
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    Cell Motility and the Cytoskeleton 1 (1980), S. 167-167 
    ISSN: 0886-1544
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 15
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    Gamete Research 3 (1980), S. 121-132 
    ISSN: 0148-7280
    Keywords: sperm nucleus ; fish oocyte ; germinal vesicle (GV) ; nuclear formation ; chromosome ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: The processes occurring from sperm penetration to chromosome formation in the cytoplasm of Oocytes matured in vitro, after removal of the germinal vesicle (GV) and before hormonal stimulation, were observed with electron microscope. The dechorionated oocytes, matured without the participation of the GV material, responded to sperm penetration by initiating a cortical reaction within 20 seconds after insemination. The pentrating sperm nuclei transformed to male pronuclei with vesiculation of the nuclear membrane, chromatin decondensation, and formation of a pronuclear membrane. Before cleavage, however, no chromosome formation was observed in these oocytes. Instead, the fully grown pronuclei change to a picnotic chromatin mass without or with an only fragmented nuclear membrane, then disappeared. On the contrary, sperm nuclei that penetrated into the cytoplasm of naked eggs containing GV material during maturation underwent pronuclear and chromosomal formation. Judging from these observation in Oryzias oocytes, the GV material seems to be unnecessary for the formation of pronucleus from the compact sperm nucleus, but is essential for the process of chromosomal formation.
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  • 16
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    Gamete Research 3 (1980), S. 179-202 
    ISSN: 0148-7280
    Keywords: Sertoli cell ; spermatogenesis ; junction ; germ cell ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
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  • 17
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    Gamete Research 3 (1980) 
    ISSN: 0148-7280
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 18
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    Gamete Research 3 (1980), S. 203-209 
    ISSN: 0148-7280
    Keywords: actin ; mitochondrial movement ; spermiogenesis ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: The presence of actin filaments around mitochondria during vertebrate spermiogenesis was demonstrated by immunofluorescence and immuno-electron microscopy and by heavy meromyosin decoration. The presence of actin is supposed to be related to mitochondrial rearrangements occurring in the spermatid stage.
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  • 19
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    Gamete Research 3 (1980), S. 133-140 
    ISSN: 0148-7280
    Keywords: rat oocytes ; maturation ; oxygen consumption ; cumulus cells ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Oocytes collected from immature PMSG-treated rats on the morning of proestrus were allowed to mature in culture either surrounded by their cumulus cells or after denudation. It was found that the time course of oocyte nuclear maturation was similar whether the cumulus cells were present or not. The oxygen consumption of noncultured oocytes was 0.12 nl/hr/oocyte and increased by 40% after four to eight hours in culture with intact cumulus. Respiration of oocytes cultured without cumulus remained constant throughout the culture, except for a transient decrease after four hours.It is concluted that the cumulus cells do not affect the spontaneous nuclear maturation in vitro, but that the metabolism in oocytes cultured with intact cumulus is different from that of cultured denuded oocytes. Furthermore, it appears that the rise in oocyte oxygen consumption is not a prerequisite for nucler maturation.
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  • 20
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    Gamete Research 3 (1980), S. 141-148 
    ISSN: 0148-7280
    Keywords: cow blastocysts ; zona pellucida ; stability and location of antigenic material ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Labeling of the zona pellucida of cow blastocysts with zona-specific anti-serum shows that antigenicity is unaffected by abnormal cleavage, in vitro culture, or frozen storage. The uniform labeling in thin sections indicates that the zona pellucida is homogeneous antigenically. Heavier labeling of the inner and outer surfaces of the zona pellucida in thick sections appers to be due to greater porosity of these regions, in which the zona material becomes highly dispersed, or even partly solubilized, thereby permitting the formation of an antigen-antibody matrix.
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  • 21
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    Gamete Research 3 (1980), S. 169-177 
    ISSN: 0148-7280
    Keywords: oviduct ; oviductal fluid ; mucin ; steroids ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Utilizing the intra-abdominal flask technique to collect oviductal fluid, the presence of two or possibly three reproductive-tract-specific antigens have been observed in rabbit oviductal fluid. Two of these antigens may be accounted for by the two forms of uteroglobin. The other antigen has a molecular weight greater than 200,000 daltons and its concentration in oviductal fluid is under hormonal control. During pseudopregnancy (PSP), when progesterone concentrations are high, or upon progesterone administration, the concentration of this high molecular weight antigen doubles in oviductal fluid. This correlates well with the previously observed increase in release of secretory products from the oviductal epithelia.
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  • 22
    ISSN: 0148-7280
    Keywords: Bryophyta ; Phaeoceros ; spermatid morphogenesis ; spermatogenesis ; ultrastructure ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: An ultrastructural examination of spermatogenesis in Phaeoceros has shown nucleoli to be present in spermatogenous cells and to persist until the centrioles become associated with nuclei of young spermatids. At the onset of multilayered structure (MLS) formation, well-defined aggregations of osmiophilic strands begin to form in the nuclei of young spermatids and disappear shortly after chromatin condensation starts in the midstage spermatids. When the centrioles in the young spermatids are orientated perpendicular to the nuclear envelope, the nucleoplasm immediately in front of them is densely stained. Where the spline tubules of the MLS extend over the nucleus, the nuclear envelope is devoid of pores, and the inner nuclear membrane is contacted internally by the local deposition of dense staining nucleoplasm. Chromatin condensation begins with strands extending perpendicularly from the dense staining nucleoplasm beneath the spline and continues with the nuclear beak becoming filled with condensed chromatin. As the MLS lamellae disappear acropetally, the rear portion of the anterior mitochondrion (AM) extends back under the nuclear beak which now narrows to a size that approximates the anterior end of the nucleus of a spermatozoid. By the end of the mid-spermatid stage, the nucleus has coiled approximately one gyre of a helix and the five or six central slpine tubules extend over the plastid which is now located beneath the front end of the AM. Several profiles of endoplasmic reticulum confluent with the nuclear envelope are present. Possible factors which might play a role in determining the morphology of the mid-spermatids are discussed.
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  • 23
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    Gamete Research 3 (1980), S. 211-216 
    ISSN: 0148-7280
    Keywords: acrosome ; human sperm ; lectin ; capacitation ; fertilization ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Because the acrosome of human sperm is too small to be directly visualized by phase-contrast microscopy, acrosome reactions (that is loss of the acrosome) are generally not evaluated in studies of human sperm capacitation and fertilization. Nevertheless, it would be useful in such studies to have a technique for easily identifying and quantitating acrosome-reacted sperm. In this paper, we describe a method for labeling the human sperm acrosome with fluorescein-conjugated Ricinus communis agglutinin-60 (FITC-RCA); we show that in sperm without acrosomal caps, FITC-RCA labeling occurs either not at all or only in the equatorial segment of the acrosome. To determine if the absence of FITC-RCA labeling in the acrosomal cap region gives a reliable estimate of acrosome reactions, washed sperm or sperm incubated in a capacitating medium (BWW) were divided into two groups, which were then fixed for FITC-RCA labeling or transmission electron microscopy. Counts of acrosome reactions made by each method were similar, and we observed an increase in the percentage of reactions following incubation in BWW. We conclude that the FITC-TCA labeling technique is a reliable method for accurately scoring the percentage of acrosome-reacted human sperm.
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  • 24
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    Gamete Research 3 (1980) 
    ISSN: 0148-7280
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 25
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    Gamete Research 3 (1980), S. 1-7 
    ISSN: 0148-7280
    Keywords: mouse ; in vitro fertilization ; inhibitors of fertilization ; calcium ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Better than 75% fertilization of C57BL/6 mouse eggs with C57BL/6 sperm is obtained in vitro in a modified Kreb's-Ringer-bicarbonate medium containing 8 mM HEPES. No fertilization of obtained when Ca2+ is omitted from this medium. The drug verapamil, which interferes with Ca2+ channels and blocks the acrosome reaction [Schackmann et al, 1978] and fertilization in the sea urchin, also blocks fertilization of mouse eggs in vitro when included in complete medium at a concentration of 80 μg/ml. Tetraethylammonium, which inhibits delayed axonal potassium currents and prevents the acrosome reaction in sea urchin sperm, also completely inhibits fertilization of mouse eggs in vitro at a concentration of 5 mM. Tetramethylammonium, which does not inhibit potassium movements at the same concentration reduces fertilization by about 50%. The data are consistent with the hypothesis that ion movements are necessary for activation of the sperm and/or egg in mouse fertilization.
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  • 26
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    Gamete Research 3 (1980), S. 17-24 
    ISSN: 0148-7280
    Keywords: sperm ; motility ; neurochemical ; paraoxon ; acetylcholine ; cholinesterase ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: The hypothesis that motility of avian sperm is regulated by acetylcholine was examined by treating rooster (Gallus domesticus) sperm with choline analogs and paraoxon, an inhibitor of colonesterases. Acetylcholine chloride (AChCl) was most effective, acetylthiocholine iodide and butyrylthiocholine iodide were less effective, and choline chloride was ineffective in stimulating sperm motility. Histochemical localization of cholinesterase activity with the electron microscope showed enzyme activity to be associated with membranes of the head and within fibrillar components of the tail. Increasing concentrations of paraoxon decreased cholinesterase activity and increased sperm motility. The data provide evidence that the motility of avian sperm, like that of mammal and sea urchins, may be regulated in part by a system with similarities to the cholinergic neurotransmitter system.
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  • 27
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    Gamete Research 3 (1980), S. 45-57 
    ISSN: 0148-7280
    Keywords: clawed frog ; egg ; fertilization ; jelly coat ; motility ; sperm ; Xenopus laevis ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: A reproducible and effective method for fertilization eggs of Xenopus laevis was developed based of systematic manipulation of environmental factors. The effects of varying concentrations of individual components of a fertilization medium were tested by measuring jelly swelling, sperm motility, and sperm longevity. Results were used to develop an improved medium for fertilization, consisting of 41.25 mM NaCl, 1.25 mM KCl, 0.25 mM CaCl2, 0.0625 mM MgCl2, 0.5 mM Na2HPO4, 2.5 mM HEPES, 1.9 mM NaOH, final pH(2°) 7.8.
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  • 28
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    Gamete Research 3 (1980), S. 247-257 
    ISSN: 0148-7280
    Keywords: spermatozoa (salmonid) ; adenosine triphosphate (ATP) in sperm motility ; cyclic adenosine monophosphate (cAMP) in sperm motility ; reactivation of trout sperm motility ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: The motility of salmonid spermatozoa initiated by dilution of the milt with ovarian fluid or isotonic saline is brief duration; it was believed that it can be activated only once in the life of the spermatozoon. Dilution of the milt with an equal volume of isotonic saline (0.12 M-NaCl) containing 5 mM-3-isobutyl-1-methylxanthine (MIX) prolonged and intensified sperm motiliy. When motility had stopped after initial mobilization with saline or ovarian fluid, it could be reactivated by addition of MIX; reactivated spermatozoa fertilized eggs. Dilution with saline containing K+ (24 mEq/liter) did not initiate sperm motility even in the presence of MIX. The spermatozoa were mobilized by subsequent with 0.12 M-NaCl. The concentration of adenosine triphosphate (ATP) in sperm suspensions dropped on dilution with saline and rose as motility ceased, but declined without subsequent recovery following dilution with MIX-saline. The concentration of cyclic adenosine monophosphate (cAMP) rose and fell sharply on initiation of motility and rose again after motility had declined. While salmonid spermatozoa can be mobilized by dilition with saline alone, the effectiveness of MIX in reactivating “spent” spermatozoa supports the assumption that cAMP plays a role in the initiation of sperm motility.
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  • 29
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    Gamete Research 3 (1980), S. 279-290 
    ISSN: 0148-7280
    Keywords: ovoperoxidase ; zona hardening ; zona pellucida ; mouse eggs ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: One consequence of fertilization or parthenogenetic activation of mammalian eggs is an altaration in the solubility proprieties of the zona pellucida, known as zona hardening. Several lines of evidence indicate that an ovoperoxidase, which is activated and/or secreted from mouse eggs. Following parthenogenetic activation, corss-links tyrosine residues in the zona pellucida and results in hardening of the zona. First, zona hardening, as determined by decreased solubility of the zona in pronase, is inhibited by several compounds known to inhibit peroxidases. Inhibitors of hardening include phenylhydrazine, sodium sulfite, sodium azide, and glycine ethyl ester. Second, tyrosine analogs inhibit zona hardening, unless the phenolic hydroxyl group or ortho position is blocked. That is, O-methyltyrosine (methyl substitution of phenolic hydroxyl) does not inhibit hardening; o-methyltyrosine (methyl substitution of one ortho position) partially inhibits, whereas tyramine and N-acetyltyrosine (free hydroxyl and ortho positions) effectively block hardening. Finally, exogenous horseradish peroxidasepromotes limited hardening of the zona in unactivated eggs. These results are consistent with a peroxidase catalyzed cross-linking of tyrosines in the zona that results in hardening of the zona pellucida.
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  • 30
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    Gamete Research 3 (1980), S. 291-298 
    ISSN: 0148-7280
    Keywords: condensed chromatin ; sperm ; Pteridium ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Nuclei of pteridium sperm have been dispersed by turbulence in natural or slightly alkaline buffer after stripping off the cytoplasm with nonionic detergent. The nuclei tended to break up into fragments arranged in a linear order. These fragments fluoresced brightly with acridine orange as did intact nuclei. Grounds are given for identifying the smaller fragments with chromosomes. It is proposed that the sperm nucleus of British Pteridium, possibly an autotetrapolid, consists of a sequence of paired homologues.
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  • 31
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    Gamete Research 3 (1980), S. 307-307 
    ISSN: 0148-7280
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
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  • 32
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    Gamete Research 3 (1980), S. 305-306 
    ISSN: 0148-7280
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
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  • 33
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    Gamete Research 3 (1980), S. 309-316 
    ISSN: 0148-7280
    Keywords: fertilization ; membrane potential ; bonellin ; amino acid incorporation into proteins ; DNA synthesis ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: We here describe further studies on the action of bonellin on sea-urchin eggs. Bonellin brings about Some of the changes that are known to occur in the egg upon fertilization. In particular, it appears to cause the increased rate of incorporation of amino acids into proteins, the increase of the voltage noise, and the exocytosis of some of the cortical granules. A comparison with the effect of ammonia is discussed.
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  • 34
    ISSN: 0148-7280
    Keywords: female meiosis ; estrogen synthesis ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: It has been suggested that the production of estrogens by the fetal ovary may modulate the entry or progression of meiosis in the female mammalian fetus. In the present study the possibility that the site of this steroid synthesis is the rete ovarii system was explored in the fetal mouse of gestational ages 12.5 to 18 days. The method of ultracytochemical localization of 3β hydroxy-steroid ferricyanide was used. Reaction product was found in the cytoplasm of the rete ovarii (prefollicular) cells as early as day 14 with increasing amounts seen at later gestational ages. The presence of this essential enzyme system in cells closely applied to oogonia and oocytes during an active meiotic period must be considered in developing concepts of meiotic entry.
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  • 35
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    Gamete Research 3 (1980), S. 351-367 
    ISSN: 0148-7280
    Keywords: marsupial ; spermatozoa ; nucleus ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Spermatozoa of six species of Australian marsupials have been studied. The nucleus is highly unstable when compared with those of eutherian mammals. When thin films of spermatozoa in buffered saline are air-dried on glass slides, the nucleus disintegrates and flattens, leaving the acrosome, midpiece, and tail intact. This spreading of the nucleus can be inhibited by seminal plasma proteins and by bovine serum albumin, but is potentiated by detergents. The nucleus also decondenses spontaneously in the presence of high concentrations (〉0.25M) of calcium and magnesium salts, leaving the head membranes, acrosome, midpiece, and tail intact. This is inhibited by EDTA. In some species, certain areas of the nucleus appear more resistant t o Ca++/Mg++ treatment, and the initial stages of decondensation are uneven. Ultrastructurally the Ca++/Mg++ dispersed chromatin shows a moderately fine, branching, fibrillar structure, interspersed with dense granules. Treatment with disulphide bond cleaving agents together with detergents results in rapid and complete dispersal of the chromatin and acrosome, and slow digestion of midpiece and tail structures. Treatment with HCl, NaCl, KCl, EDTA, detergents, and sucrose has no effect on nuclear integrity, but treatment with NaOH (0.9-1.0M) results in complete digestion of the whole sperm. These findings are discussed in the light of evolutionary differences between marsupial and eutherian mammals in terms of sperm structure and composition.
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  • 36
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    Gamete Research 3 (1980), S. 369-377 
    ISSN: 0148-7280
    Keywords: yolk ; preimplantation embryo ; ultrastructure ; hamster ; mouse ; rat ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Yolk material of preimplanation stages of embryos of the hamster, mouse, and rat were examined by a standardized electron microscopical procedure. The material was encountered as fibrils, scattered more or less densely in the cytoplasm. In the hamster, the material was present in large masses and the fibrils had a chain-like appearance when cut longitudinally. The ultrastructure of the fibrils was compatible with a helical pattern. The fibrils had a width of about 40 nm and the pitch (the axial distance of the repeating unit) was about 30 nm. In the mouse, the yolk material was dispersed in the cytoplasm forming small plaque-like groups. Also, in this species the fibrils were chain-like but smaller than in the hamster. The fibrils were often closely situated, resulting in images with varying crystalline appearances. In the rat, the yolk appeared as light areas occupying a substantial part of the cytoplasm. The fibrils in the yolk plaques were sparse and diffusely outlined. They were thinner than the fibrils of the mouse-yolk material, did not display any helical pattern at the resolution used, but showed a periodicity.
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  • 37
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    Gamete Research 3 (1980), S. 405-406 
    ISSN: 0148-7280
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
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  • 38
    ISSN: 0148-7280
    Keywords: sperm-zona contact ; fertilization ; peptides ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: An investigation was made as to the nature of two of the factors, termed S1, released within the first 30 minutes after contact is made between capacitated hamster sperm and the zona pellucida in vitro. Previous studies showed that these S1 factors were detected two and 20 to 25 minutes after the gametes were combined and that, based on filtration studies, the former possessed a molecular weight of less than 5,000 daltons. The present results show that the quantity of the 20-25-minute S1 factor released into the supernatant increased linearly as a function of the sperm concentration. This factor passed unimpeded through a filter with a 5,000 molecular weight cutoff but only 42% of the activity traversed a filter with a cutoff of 2,000 daltons. The two-minute S1 factor, in the virtual total absence of cells, was stable for 10 to 15 minutes, but lost significant activity upon longer incubation. Under the same conditions, the 20-25-minute factor lost approximately 25% of its activity within 15 minutes, but remained stable at this level for at least 45 minutes of incubation. Both S1 factors were not affected by a mixture of glycosidases, but were inactivated by subtilisin, trypsin, and leucine aminopeptidase which was contaminated with endopeptidases. The activity of the two-minute S1 factor appeared more susceptible to the action of the proteases than that of the 20-25-minute S1 factor. In contrast to previous results obtained with the two-minute S1 factor, the release of the 20-25-minute S1 factor was not inhibited by the inclusion of soybean trypsin inhibitor a t concentrations which are known to inhibit penetration of the zona by the sperm. The results suggest that the two- and 20-25-minute S1 factors are peptides which are not identical.
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  • 39
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    Gamete Research 3 (1980), S. 343-349 
    ISSN: 0148-7280
    Keywords: Sperm ; capacitation ; mouse strain differences ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Intial in vivo studies were performed to observe the proportion of eggs fertillized at specific intervals after natural mating and ovulation in our research mouse colony. Proestrous females of the C57BL/10Wt, SJL/Wt inbred strains and the F1 hybrid cross (B10 × SJL or reciprocals) were paired in the after-noon with males of their respective strain and examined for vaginal plugs at the midpoint of the dark period (2400 hours). Oviducts were periodically collected from mated females, and ovulation was first observed at 4, 5.2, and 3 hours after 2400 hours in the B10, SJL, and F1 hyrid, respectively. The clutch of eggs from each ovulating female, was placed in culture, and cleavage oviduct lavage verifying female mating was placed in culture, and cleavage was used as the criterion for fertilizaition. Fifty percent of the eggs were fertilized 2.2, 5.0, and 2.5 hours after ovulation in B10, SJL, and F1 hybrid females, respectively. Because twice the legth of time was required to fertilize a similar proportion of eggs from the SJL strain as the F1 hybrid, these two strains were used for determining their rate of fertilization under more fully controlled conditions in vitro. Forty-nine percent of F1 hybrid eggs were fertilized after 4 hours incubation with SJL epididymal sperm, whereas 53% fo SJL and 56% of F1 hybrid eggs were fertilized after only 2 hours incubation with F1 hybrid epididymal sperm. Thus, using sperm from these two mouse strains, the amount of time required to fertilize approximately 50% of the eggs within a clutch both in vivo and vitro was very similar. These observations demonstrte teh validity of using this in vitro system for fertilization studies and confirm that the temporal events in sperm capacitation and egg penetration are dependent on the genotype of the sperm. Similarities in fertilization rates at specific times after ovulation or insemination in vitro imply that the initiationof sperm capacitation in vivo occurs near the time of ovulation and several hours after mating. We tentatively suggest that follicular fluid may be required for completion of mouse sperm capacitaiton in vivo.
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  • 40
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    Gamete Research 3 (1980), S. 379-393 
    ISSN: 0148-7280
    Keywords: aging ; ova ; acid phosphatase ; superovulation ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Morphological and cytochemical (acid phosphatase) changes associated with mouse ova and cumulus cells aged within the oviducts (in vivo) or in culture (in vitro; 1-24 hours postovulation) have been investigated. Structural alterations of cumulus cells were apparent immediately after ovulation and included nuclear pycnosis and cytoplasmic vacuolization. Nevertheless, approximately 30% of the cumulus masses examined contained cells that plated out when cultured and remained viable for up t o three days in vitro. From 12 t o 24 hours postovulation almost all cumulus cells of specimens aged in vivo showed signs of degeneration. Disruption of the meiotic spindle and an increase in acid phosphatase positive organelles were characteristic of in vivo and in vitro aging ova. The percentage of fragmented eggs obtained from super-ovulated (5 IU PMS followed by 5 IU HCG) mice approximately one and 24 hours postovulation was not significantly different. Eggs obtained from superovulated animals and aged in vitro for 24 hours yielded significantly more fragmented ova. Fragmented eggs were not obtained from cycling females on the morning of estrus. When such eggs were cultured in vitro for 24 hours the percent fragmentation was significantly lower than that for aged eggs obtained from super-ovulated mice. These results indicate that 1) similar morphological alterations occur among cumulus cells and eggs aged either in vitro or in vivo, 2) ova from superovulated mice do not constitute a homogeneous population and 3) the method of superovulation employed in this study induces the ovulation of a relatively large group of eggs that are susceptible to fragmentation when cultured in vitro.
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  • 41
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition of small amounts of [Gd(2 : 2 : 1)]3+ cryptate to aqueous solutions containing 111Cd2+ or formamide decreases metal nuclide or nitrogen-15 spin-lattice (T1) relaxation times without affecting cadmium or nitrogen chemical shifts. This cryptate is thereby demonstrated to have substantial promise for greatly decreasing the time necessary to obtain natural abundance metal nuclide or 15N NMR spectra with satisfactory signal-to-noise ratios for many compounds with long metal or 15N relaxation times.
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  • 42
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    Organic Magnetic Resonance 13 (1980), S. 89-91 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Analysis of the 13C NMR spectra of a series of 2,3-dihydro-1H-pyrrolo[1,2-c]imidazole derivatives has provided chemical shift data for (˜184 ppm), (˜173.5 ppm), (˜158 ppm) and (˜148 ppm) groups. A full analysis of the 13C chemical shifts of the C atoms of the pyrrole ring and of an N-phenyl substituent is described.
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  • 43
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    Organic Magnetic Resonance 13 (1980), S. 105-109 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemical shifts and substituent chemical shift (SCS) effects are reported for 21 monosubstituted iso-quinolines, carrying a halogeno, amino, piperidino or ethoxy group in position 1, 3 or 4. In some cases, assignments of 13C resonances were based on the spectra of the corresponding 5-deutero derivatives. For the fluoroisoquinolines some 13CF coupling constants are given. The 13C NMR spectra of 15 disubstituted isoquinolines were measured; with a few exceptions, mainly the 3,4- and 1,4-disubstituted isoquinolines, the chemical shifts agreed well with those calculated by addition of the SCS effects.
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  • 44
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    Organic Magnetic Resonance 13 (1980), S. 110-113 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: One methyldecahydroisoquinoline and some octahydro- and decahydro-isoquinolone derivatives were studied by 13C NMR. The configuration of these products was deduced by comparison of the experimental chemical shifts and the calculated values. Conclusions could thus be reached on the configuration of related 8,13-diazasteroids in the 19-norandrostane series.
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  • 45
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    Organic Magnetic Resonance 13 (1980), S. 114-115 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon-13 chemical shift assignments have been obtained for the naturally occurring Cephalotaxus alkaloids, cephalotaxine, acetylcephalotaxine, harringtonine, isoharringtonine, drupacine and cephalotaxinone.
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  • 46
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    Organic Magnetic Resonance 13 (1980), S. 116-118 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Calculations of the dependence of 13C chemical shifts on the dielectric constant, ∊, of the medium are reported using the INDO/S parameterized version of Pople's method together with the solvaton model. Satisfactory agreement with the available experimental data is obtained. The rather sensitive dependence of chemical shift upon ∊ suggests that polar solute - solvent interactions in aprotic media should be taken into account when considering 13C chemical shifts.
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  • 47
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    Organic Magnetic Resonance 13 (1980), S. 119-121 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C T1ρ values measured for N,N-dimethylpiperidinium iodide yield activation parameters (ΔH≠ and ΔG270≠ values of 43.7 and 41.6 kJ mol-1) for the chair-chair interconversion in aqueous solution similar to those measured for 1,1-dimethylcyclohexane. The potential of 13C T1ρ values for studying dynamic processes in aqueous solutions is illustrated.
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  • 48
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    Organic Magnetic Resonance 13 (1980), S. 122-125 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equimolar mixtures of typical lanthanide shift reagents such as Eu(fod)3, Pr(fod)3 or Yb(fod)3 with silver trifluoroacetate, previously used to induce paramagnetic shifts in the 1H NMR spectra of alkenes, have been successfully applied to simple aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylenes. In benzene and p-xylene the signals of all the aromatic protons are shifted identically. In other substituted benzenes the magnitude of the induced shift depends on the distance between the proton and the substituents. In addition, the different behaviour of the signals of the methyl groups in meta-and para-xylene on the addition of the complex shift reagent allows the quantitative analysis of the two xylenes in their mixtures.
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  • 49
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    Organic Magnetic Resonance 13 (1980), S. 126-131 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C and 15N spectra of unsymmetrically N-substituted formamides and alkyl-, substituted alkyl-, and arylcarboxamides, which can be considered as model peptide compounds, were determined and discussed in terms of nitrogen lone pair delocalization. Differential solvent shifts and through-space steric effects are considered as a tentative explanation of the difference in screening between geometrical diastereoisomers. Z-E assignment and the thermodynamic stability of diastereoisomers can also be predicted in some circumstances from a consideration of the 15N chemical shifts. Data concerning small peptides are discussed in the light of the results obtained using the model compounds.
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  • 50
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    Organic Magnetic Resonance 13 (1980), S. 132-136 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 13C chemical shifts of twenty chloro- and nitro-substituted phenols have been measured in d-chloroform. The influence of substituents on the screening at C-1, on the total charge at this position and on the dipole moments is reported and analysed. The results of this study suggest that variations of the chemical shifts at C-1 for meta-methyl-, meta-chloro-, meta-nitro-, ortho- and para-methyl-, ortho- and para-chlorosubstituents mainly reflect charge density changes. The influence of ortho-nitro groups on the screening of C-1 is more complex.
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  • 51
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alterations have been introduced in the semi-empirical INDO parameters in order to study their influence on the Fermi contact term of the indirect spin-spin coupling constants as calculated by the finite perturbation theory (FPT). For this purpose a set of molecules containing hydrogen, carbon and/or fluorine has been selected. In general, most coupling constants are found to be much more sensitive than other molecular properties to small changes in the INDO parameters. This sensitivity depends strongly on the particular calculated coupling constant. In most cases the uncertainty in the INDO parameters leads to uncertainties in the coupling constants which are much greater than their experimental errors.
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  • 52
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    Organic Magnetic Resonance 13 (1980), S. 143-147 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two resonance lines were observed in 2,6-dichlorobenzamide, both in liquid nitrogen and at room temperatures, using a self quenched super-regenerative NQR spectrometer. Analysis of the Zeeman effect on the two lines using an uncut crystal grown from solution reveals: (1) the crystal belongs to the orthorhombic system; (2) there are two crystallographically equivalent but physically non-equivalent directions for the principal field gradient making an angle of 71° for the low frequency line, and four such directions for the high frequency line; (3) the directions of the crystalline axes a, b and c are tentatively fixed as (90°, 90°), (90°, 90°) and (0°, - ); (4) from morphological studies a: b: c are estimated as 0.959 ± 0.005: 1:1,402 ± 0.005 and, from the estimated density (1.440 gms/cc) of the crystal, the absolute values a, b, c are calculated, on the basis of four molecules per unit cell, as a = 8.33 Å, b = 8.68 Å and c = 12.18 Å; (5) there are a mininium of four molecules per unit cell; the four molecules lie in four different planes which are, however, connected by symmetry operations. There is an inplane bending by 6.5° between the two C—Cl bonds away from one another and (6) the ionic, single bond and double bond characters for both chlorines are almost equal and are in the ratio 25:72:3.
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  • 53
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    Organic Magnetic Resonance 13 (1980) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 54
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    Organic Magnetic Resonance 13 (1980), S. 1-8 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied the dynamics of binding of 19F labelled haptens by mouse plasmacytoma antibody MOPC-315, a protein which shows specificity for nitrophenyl haptens. The off-rates for the dissociation of hapten from MOPC-315 proteins (7S, Fab′ and Fv) were determined by the application of several methods including a technique which, in certain cases, allows the direct determination of the rate of exchange of nuclei between magnetically non-equivalent sites without requiring prior knowledge of intrinsic line widths. Used in conjunction with independently determined data on line widths, chemical shifts, and binding affinities, these studies show that the rates for hapten association to, or dissociation from, the intact 7S antibody, the Fab′ fragment, and the Fv fragment of MOPC-315 are essentially the same. They also indicate the presence, probably in the Fv region, of a low affinity (K∼ 103 M-1) site(s) for hapten binding. The mobility of the hapten combining site decreases as the size of the protein increases. These rate data, which were determined at relatively high protein concentrations (up to 40 mg ml-1), agree with on-rates determined at much lower protein concentrations (≤1 mg ml-1); we therefore conclude that protein aggregation, if it does occur, does not significantly affect binding in these systems.
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  • 55
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    Organic Magnetic Resonance 13 (1980), S. 9-13 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study has been made of the 13C chemical shifts of a number of acyclic alkanes, alkenes, nitriles and ketones which contain quaternary carbon atoms. Similar data have also been obtained for the series of compounds involved in the synthesis of triisopropylacetic acid. Substituent effects and steric factors in these highly substituted compounds are discussed in relation to the chemical shifts.
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  • 56
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    Organic Magnetic Resonance 13 (1980), S. 193-196 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 13C NMR spectra of cyclobutane and seven methylated homologs and of ethyl cyclobutanecarboxylate and five isomeric diethyl cyclobutanedicarboxylates are reported and substituent parameters for methyl groups in methylcyclobutanes are calculated. Of note is a sizeable and nearly configuration-independent upfield shifting γ-effect.
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  • 57
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    Organic Magnetic Resonance 13 (1980), S. 197-199 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Geminal 15N—13C coupling constants have been measured in a series of 15N-enriched 1-phenyl-3,5-dialkyl-substituted pyrazoles. The importance of the orientation of the nitrogen lone-pair in determining the magnitude of 2J(15N13C) values is reflected in the enhanced coupling observed for those carbon atoms lying close in space to the lone-pair electrons.
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  • 58
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    Organic Magnetic Resonance 13 (1980), S. 200-209 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two-bond C,H coupling constants for the coupling pathways C_=C—H_ (type I) and (type II) have been studied in a variety of mono-, di- and trisubstituted ethylenes. For 2J(CH) of type I, additive increments have been determined for 20 substituents, which allow a satisfactory calculation of coupling constants, including relative signs, in di- and trisubstituted ethylenes. Several applications for E/Z isomers are presented. In cyclic compounds a positive coupling increment, δJ, is observed in going from 6- to 5-membered ring compounds.
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  • 59
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    Organic Magnetic Resonance 13 (1980), S. 26-27 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The carbon-13 NMR spectra have been recorded for representatives of three previously unexamined classes of pentacyclic triterpenes - lupanes, fernanes and arboranes. In addition to the spectra of lupeol methyl ether, cylindrin and arundoin, the spectra of a number of other triterpene methyl ethers are also recorded. The effect of methyl ether formation on the shilding values for carbons in the 3β-hydroxy-4,4-dimethyl- ring A system is defined.
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  • 60
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    Organic Magnetic Resonance 13 (1980), S. 28-32 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The carboxyl substituent effects for branched carboxylic acids have been determined by carbon-13 Fourier ransform nuclear magnetic resonance of eighteen measured and reported branched acids. For α-branched systems the substituent effects are α = 15.3 ppm, β = 2.6 ppm, γ = -1.9 ppm, δ = 0.9 ppm and ε = 0.5 ppm. For other branched acids, the determined carboxyl substituent effects are α = 19.2 ppm, β = 2.1 ppm, γ = -1.4 ppm, δ = 0.6 ppm, and ε = 0.6 ppm.
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  • 61
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The proton spectra of the compounds propene (1) and 3-methylbutene-1 (2) have been measured in various solvents and, as neat liquids, at variable temperature. The effects of solvent and temperature on 1 are found to be small, but not negligible. The effect of temperature on the coupling constants of 2 are more pronounced, which is explained in terms of an anti-gauche equilibrium. To obtain a consistent ΔE° value from each temperature dependent coupling constant it is necessary to correct for the non-conformational temperature effects (obtained from 1) as well as to correct for changes in the geometry of the entire molecule, which are concurrent with a conformational transition. Such geometry changes have been calculated by a consistent force field technique, which, when coupled with INDO-MO calculated dependencies of coupling constants on valence (and torsional) angles, provided the changes in coupling constants. The observed temperature dependence of the coupling constants of the H2C=CH -  moiety of 2 could be satisfactorily explained in this fashion. The difference in energy between the anti and gauche forms of 2 were determined as ΔE° = 127 ± 14 cal mol-1.
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  • 62
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    Organic Magnetic Resonance 13 (1980), S. 40-44 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Doublets can be observed for carbons α and β to the hydroxyl in aliphatic alcohols containing equimolar amounts of OH and OD dissolved in (CH3)2SO containing CaSO4 desiccant. Isotopic doublets are also observed for the ipso and ortho carbons in alkyl substituted phenols. Para isotopic doublets are observable in para-substituted phenols containing a large 2-substituent. The isotope shift is positive (low field) for the para carbon, opposite to the negative shifts usually observed.
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  • 63
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    Notes: Various cyclodipeptides containing glycine, alanine, leucine, valine, phenylalanine, phenylglycine and sarcosine units were synthesized by cyclization of dipeptide pentachlorophenyl esters. The 13C and natural abundance 15N NMR spectra of these heterocycles were measured in trifluoroacetic acid and compared with the spectra of the corresponding amino acids and polypeptides. The 13C NMR carbonyl signals of all cyclodipeptides show a 1.5-4.0 ppm upfield shift relative to the corresponding polypeptides. The 15N NMR signals show no such consistent relationship. The substituent effects and the neighbouring residue effects observed in the 15N NMR spectra of the cyclodipeptides are different from those of polypeptides, while the one bond N—H coupling constant of cis and trans amide groups was almost identical. The nitrogen and the carbonyl signal of the Gly units in cyclo-Gly-Phe show an extraordinary downfield shift, reflecting the interaction of the phenyl group with the 2,5-dioxopiperazine ring.
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  • 64
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
    Notes: In order to separate inductive and lone pair effects on geminal and vicinal coupling constants in a stereochemically well-defined system, the 1H NMR spectra of phenylcyclopropane (1), N-methyl-2-phenylaziridine (2), styrene oxide (3) and 1,1-dimethyl-2-phenylaziridinium fluorosulfonate (4) were compared. In D2O the heterocyclic ring protons of 4 were split into an ABX pattern which gave J(cis) = 8.5, J(trans) = 7.4 and J(gem) = -4.8 Hz (signs consistent with INDOR results). From the small solvent effects on J(vic) determined from 4-d1, it was concluded that J(gem) is -5.0 ± 1.0 Hz in methylene chloride. The absolute values for the coupling constants for 1 and 4 provide a measure of the inductive effect of the ring hetero group on J. Values of J(gem) for 2 and 3 deviated from those predicted on the basis of the above inductive effect, suggesting lone pair contributions to J(gem) of c. +5.5 Hz per lone pair. With this estimate it was possible to predict accurately the J(gem) values for 2-t-butyloxaziridine and 1-t-butyldiaziridine. The values of J(cis) and J(trans) for 2 and 3 likewise suggested a contribution of -2.5 Hz to J(cis) and -2.7 Hz to J(trans) per lone pair. The present results suggest that the major factors causing positive J(gem) values in epoxides and aziridines are increased s character to the C—H bonds and lone pair effects, while the so-called electronegativity effect actually operates in the opposite direction to decrease J(gem). Also, the unusually low J(vic) values of epoxides relative to cyclopropanes are now seen to be due more to negative lone pair contributions than to the electron withdrawing ability of oxygen.
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    Organic Magnetic Resonance 13 (1980), S. 59-62 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An individual assignment of certain peaks in the proton and 13C NMR spectra of bilirubin and of bilirubin dimethyl ester is described. The assignment was achieved through the spectra of vinylneoxanthobilirubinic acid and by off-resonance decoupled 13C spectra of bilirubin dimethyl ester. The signals due to the endo and exo vinyl groups were separately assigned. This assignment allows a rational interpretation of previously obtained spin-lattice relaxation times of the vinyl carbon peaks. The two vinyl groups are found to differ considerably in their motional correlation time.
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  • 66
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    Topics: Chemistry and Pharmacology
    Notes: cis(1-H, 8a-H)-1-Methylperhydro-oxazolo[3,4-a]pyridine and cis(1-H, 8a-H)-1-methylperhydrothiazolo[3,4-a]pyridine both adopt exclusively the trans-fused conformation in carbon tetrachloride solution at room temperature. Both parent unsubstituted systems exist under similar conditions as equilibria containing c. 67% (oxazolo compound) and 64% (thiazolo compound) of the trans-fused conformation. In marked contrast to these similar positions of conformational equilibria in both systems the trans(1-H,8a-H)-1-methylperhydrooxazolo[3,4-a]pyridine exists as c. 73% trans-fused in equilibrium with a cis-fused conformation whereas the trans(1-H, 8a-H)-1-methylperhydrothiazolo[3,4-a]pyridine exists almost exclusively in a cis-fused ring conformation. These differences in conformational equilibria are explained in terms of changes in non-bonded interactions.
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    Organic Magnetic Resonance 13 (1980), S. 72-74 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 13C and 31P NMR spectra of the triply 13C labelled tribenzoylphosphine [] oriented in a nematic phase have been recorded. From the spectral analysis one obtains the average CPC valence bond angle value (95.9°± 0.2), and the phosphorus chemical shift anisotropy Δσ(σ∥ - σ ⊥) which is equal to 75 ± 15 ppm.
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  • 68
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    Topics: Chemistry and Pharmacology
    Notes: Proton-coupled nitrogen-15 NMR spectra of urea, N-methylurea, N,-N′-dimethylurea, N-methyl-N′-benzylurea and N-phenylurea have been obtained at natural abundance level in neutral, basic and acidic solutions at 25°C. Base-catalyzed N—H proton exchange of the —NH2 group of N-methylurea in water was found to be 1.5 times faster than that for the -NH- group, while the corresponding acid-catalyzed exchange is 7.5 times faster. Comparison of urea and N,-N′-dimethylurea in water shows urea to be 10 times faster in base but 2 times slower in acid. The ratio of the base-catalyzed N—H proton exchanges of the two -NH- groups of N-methyl-N′-benzylurea in dimethyl sulfoxide is close to unity, whereas the CH3NH- group exchanges 4 times faster in acid. Similarly, the C6H5NH- group of N-methyl-N′-phenylurea exchanges 50 times faster than the CH3NH- group in base and about 3 orders of magnitude slower in acid. The results are rationalized by consideration of steric and electronic effects.
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    Organic Magnetic Resonance 13 (1980), S. 75-76 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The vicinal coupling constant, J(12), between the vinyl CH and the ring CH protons in vinylcyclohexane was calculated from a ‘partial molecule’ six-spin system. The 100 and 270 MHz results are in good agreement; those at 60 MHz were, however, still inaccurate in this approximation. J(12) increases with increasing solvent polarity and decreasing temperature. The energy difference between the s-trans and gauche conformers in both C2Cl4 and perdeuterioacetone solvents is 879 ± 167 J mol-1 (210±40 cal mole-1). The s-trans conformer is the most stable, in contrast to the isoelectronic cyclohexylcarboxyaldehyde where the gauche rotamers are lower in energy.
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    Organic Magnetic Resonance 13 (1980), S. 306-307 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 31P chemical shifts in N-aryliminotriphenylphosphoranes and the corresponding N-methylated phosphonium salts are presented. They can be correlated with those theories of the bonding in phosphorus-nitrogen ylides which involve partial double bonding as a result of pπ-dπ overlap.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
    Notes: An additivity relationship of substituent effects on the formyl proton chemical shift has been tested with ten disubstituted benzaldehydes. In most cases it is found that the formyl proton chemical shift, extrapolated to infinite dilution in nitromethane, is in good agreement with that calculated using the additivity relationship.
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    Organic Magnetic Resonance 13 (1980), S. 310-311 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of a 3,3-dimethyl-1,2-dihydroisoquinolin-4(3H)-one with a benzyl Grignard reagent gives a 4-benzyltetrahydroisoquinoline in which the signal of a 6-methoxy group suffers a large upfield shift in the 1H NMR spectrum, whereas a 7-methoxy group is relatively unaffected. This effect can be used to determine whether an RO-substituent is in the 6- or 7-position and, in particular, to distinguish isomeric derivatives with different RO-groups in the 6- and 7-positions. The method will allow the mechanism of cyclization of 3,4-dimethoxybenzylaminoacetonitriles to be more fully elucidated.
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    Organic Magnetic Resonance 13 (1980) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Organic Magnetic Resonance 13 (1980), S. 313-318 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation of some 2-σ-1,3,2-dioxaphospholanes (σ=OAlkyl, CI) is studied. The determination of the 2J(POC) and 3J(POCC) coupling constants, which are influenced by the bulk of the alkoxy group, is a means of obtaining information about the rotation around the P—OR bond, which is dependent on steric interactions between the phosphorus lone pair, the alkoxy group and the substituents on the ring. When σ is a tert-butoxy group, a direct ‘through-space’ interaction is found between the phosphorus atom and one of the primary carbons of the OR group. If there is no substituent on the ring, the 31P chemical shifts are little affected by changes in OR; a diamagnetic effect is observed, however, in the case of the tert-butoxy group which is enhanced for the 4,4,5,5-tetramethyl derivatives.
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    Organic Magnetic Resonance 13 (1980), S. 319-322 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An important 13C NMR shielding effect on carbons bearing a heavy chalcogen is demonstrated. This effect is parallel to that induced by iodine, but to a lesser extent. For acyclic compounds and for partially saturated heterocycles, there is an excellent linear correlation between the 13C chemical shifts of carbons bearing a chalcogen and carbons bearing a halogen atom in the corresponding compound. The linearity of the relationship is less satisfactory with heteroaromatic compounds.
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    Organic Magnetic Resonance 13 (1980), S. 328-329 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The composition of the mixture from the reaction of the basic amino acids ornithine or lysine with pyridoxal-5′-phosphate was investigated in D2O by 1H NMR and was found to be dependent on pH, α attack being favoured at acid pH and ω attack in basic solutions.
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  • 77
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    Topics: Chemistry and Pharmacology
    Notes: The changes in chemical shift induced by isomerization for all the ring protons of the Z- and E-5,5-dimethyl-2-cyclohexenylidene acetonitriles depend only on the through-space effects of the cyano group. The configurational assignments were made taking into consideration the anisotropic and electric field effects, either separately or together. In the first case, the total effects are ΔXCNT=-14.7×10-6cm3 mol-1 and bμCNT=14.7×10-30 cm3, respectively. The second approach allows the estimation of the values ΔXCN=-4.9 × 10-6 cm3 mol-1 and bμCN=9.8 × 10-3 cm3, reflecting the combined contributions of magnetic anisotropy and electric field to the total effect.
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    Organic Magnetic Resonance 13 (1980), S. 330-334 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C NMR spectroscopic data are reported for the s-triazolo-as-triazinones of five isomeric series. Comparison of their 13C chemical shifts and CH coupling constants allows the determination of the type of ring junction of the two heterocycles, as well as the predominant tautomeric form in each system.
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  • 79
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    Topics: Chemistry and Pharmacology
    Notes: The natural abundance 15N NMR spectra of glycylglycine and alanylalanine derivatives with various N- or O-protecting groups were measured in dimethyl sulphoxide, pyridine and fornic acid. The nitrogens directly attached to the protecting group have chemical shifts relative to NO3- in the range -220 to -358 ppm. The influence of the amino end group on the next peptide nitrogen (Gly-Gly bond) amounts to, at most, 1.7 ppm. The influence of the O-protecting group is also weak (Δ δ≤2 ppm), but strongly dependent on the solvent.
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    Organic Magnetic Resonance 13 (1980), S. 343-344 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon-13 NMR spectra of solid polycrystalline bicyclo[3.3.1]nonan-9-one and adamantanone have been measured at 315K. The relatively narrow 13C linewidths observed for these solids, together with measured spin-lattice relaxation times, indicate that both these solids are orientationally disordered. Observed 13C chemical shifts of solid bicyclo[3.3.1]nonan-9-one indicate a twin-chair conformation for the two cyclohexanone rings.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Assignment of the carbon resonances in nine derivatives of N-hydroxybenzotriazole has been carried out. The 13C NMR method enables tautomeric N-hydroxy and N-oxide and isomeric O- and N-acyl structures to be identified. In DMSO, the predominant tautomer of N-hydroxybenzotriazole was found to be the N-hydroxy form. The structure of the benzoate and methyl and phenyl carbonate esters were likewise established, but for the two latter compounds, hydrolysis of the equilibrating O- and N-acyl isomers imposed some limitations on the usefulness of the technique.
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    Organic Magnetic Resonance 13 (1980), S. 345-348 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C NMR spectra of six kawa-pyrones (styryl α-pyrones) have been assigned. The assignments are based on the splitting pattern in the coupled spectra, comparison of the chemical shifts with those of model compounds and by application of additivity relationships. The 13C NMR of styrene was also reinvestigated.
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    Organic Magnetic Resonance 13 (1980), S. 349-353 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemical shifts at infinite dilution and coupling constants of some meta-substituted nitrobenzenes (C6H4NO2X) were determined in CDCI3 solutions (X = CHO, OCH3, CI, Br, NH2, NO2) and in CCI4 solutions (X = OCH3, CI, Br). Substituent effects on the chemical shift of the meta-hydrogen are analysed in terms of existing theories.
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    Topics: Chemistry and Pharmacology
    Notes: Direct and long-range 13C—1H coupling constants are presented for the enone moieties of cyclopent-2-enone, cyclohex-2-enone and their protonated derivatives. A correlation is given between the experimental values and the results of quantum chemical calculations (CNDO/2, INDO). The existing calculations are modified in order to improve the relationship between the calculated and experimental results.
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  • 85
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    Organic Magnetic Resonance 13 (1980), S. 359-362 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complete rα-structure of dimethylmercury in the nematic ZLI 1167 liquid crystal was determined. This study confirms the earlier results, indicating that the structure is practically independent of the liquid crystal solvent, although some minor deviations exist. The Hg—C distance was found to be 207.97±0.05 pm, when the vibration corrections in the dipole-dipole coupling constants were taken into account. This is rather similar to the distances obtained with other spectroscopic methods. The anisotropies of the 1H and 199Hg chemical shifts were obtained by using a smectic liquid crystal and recording the corresponding spectra, the optical axis being parallel with or perpendicular to the external field direction. The experimental ratio-2.007±0.017 of the D∥ (HgH) and D⊥ (HgH) coupling constants proves that the indirect contributions in these coupling constants are negligible. Shielding anisotropies of 3.70±0.3 ppm and 7325±55 ppm for 1H and 199Hg, respectively, were obtained.
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  • 86
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon-13 spectra of twelve chlorofluoropyridines (C5CInF5-nN), of known structure, have been assigned and an assessment has been made of the degree of additivity of substituent chemical shifts (SCS). Reasonable additivity is observed for pyridine derivatives but little regulatiry can be inferred from the spectra of perchlorinated-diazines and -triazines. There is an approximately linear relationship between 13C and 19F chemical shifts.
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  • 87
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    Organic Magnetic Resonance 13 (1980), S. 368-371 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general equation describing the effect of substituents on α-carbons in a saturated framework was developed from 13C chemical shifts obtained under uniform conditions for selected aliphatic compounds. Experimental correlations for β- and γ-carbons and a discussion of the results are presented.
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  • 88
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    Organic Magnetic Resonance 13 (1980), S. 376-379 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1H NMR spectral parameters of all eight 1,2-diacetoxy-3,4-dimethylcyclopentanes and 1,2-diacetoxy-4-t-butyl-3-methylcyclopentanes are discussed.
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  • 89
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    Organic Magnetic Resonance 13 (1980), S. 380-383 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Semi-empirical calculations of dihydropyran conformations have been performed using a Karplus-type equation with the sum of chemical shifts as a correction parameter. A graphical method has been proposed to evaluate the conformational state of the molecules.
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  • 90
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon-13 NMR spectra of a number of (-)-ent-kauranoids have been studied. An unambiguous selfconsistent assignment of resonances has been made by considering the changes in chemical shifts produced by the change of substituent(s).
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  • 91
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The proton-coupled nitrogen-15 NMR spectra of hydrazinecarbothioamide and 4-methylhydrazinecarbothioamide have been taken at the natural-abundance level in neutral, basic and acidic solutions at 25°C. The N—H proton-exchange reactions of the hydrazino-NH2 groups in both compounds were found to be very rapid in the presence of acid, but quite slow in the presence of base. The hydrazino-NH protons of hydrazinecarbothioamide exhange six times and 200 times faster than the amide protons in the presence of either base or acid, respectively. Similarly, acid- and base-catalyzed N—H proton exchanges of the hydrazino-NH group of 4-methylhydrazinecarbothioamide were found to be two to three orders of magnitude faster than those of N-methylamido protons. These results can be rationalized by consideration of the effect of the lone pair on the hydrazino—NH2 group on the reactivity of the adjacent —NH— group.
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  • 92
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    Organic Magnetic Resonance 13 (1980) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 93
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The proton-coupled 13C NMR spectrum of salicylaldehyde was analysed. The second-order character of the seven independent sub-spectra allowed the signs of most of the couplings to be determined. The input values for the analyses were obtained from the known J(CH) values of benzene, phenol and benzaldehyde using the additivity principle. In most instances, very good agreement between the calculated and observed values was obtained. Significant couplings of the ring carbons to both the aldehyde and hydroxyl protons were also observed. The magnitude of these couplings was very dependent on the stereochemical relationships between the coupled nuclei.
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  • 94
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C NMR of diastereoisomeric pairs of 2,3-diaryl-2-methylbutyronitriles revealed a difference in the chemical shift of the carbon atoms between the diastereoisomers and the observed shifts were greatly influenced by the presence of an ortho substituent in the 3-phenyl ring.
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  • 95
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    Organic Magnetic Resonance 14 (1980) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 96
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    Organic Magnetic Resonance 14 (1980), S. 76-77 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Coupling constants between 11B and 13C, 13C and 1H, and 11B and 1H were obtained for LiB(CH3)4 in 1,2-dimethoxyethane, in which the anion B(CH3)4- is belived to exist as a separate ion pair. The correlations of the coupling constants with the effective nuclear charge of boron, and with the s character of the B—C bond, are discussed.
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  • 97
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    Organic Magnetic Resonance 14 (1980), S. 79-85 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C chemical shifts for a series of substituted nitronaphthalenes have been obtained by several assignment techniques. Deviations from additivity are mainly observed in the ortho-disubstituted compounds and are due, in part, to the variations of the anisotropic terms for the substituents studied.
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  • 98
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    Organic Magnetic Resonance 14 (1980), S. 86-91 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon-13 NMR signals of the biologically active norditerpenoid dilactones from Podocarpus plants were fully assigned by using selective 1H decoupling, coupling constants (2JCH), spin-lattice relaxation times (T1) and correlation of the spectra of more than thirty dilactone congeners. The spectra of five nagilactones, B, C, D, E and F, which constitute representative members of three major structural types of the dilactones: (A) 8:14, 9:11-dienolide (α-pyrone) type, (B) 7α:8α-epoxy-9:11-enolide type, and (C) 7:8,9:11-dienolide type, were extensively analysed. Some characteristic steric interactions for the substituents on the ring system can be demonstrated from the spectral properties.
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  • 99
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An ESR method for studying the mechanism of H-transfer reactions between H-donors of different reactivity (A1H, A2H…) and their free radicals (A1; A2.…) in non-polar solvents at ambient temperature is presented. The new technique is based on a pulsed initiation of various secondary phenoxy or nitroxy radicals in binary mixtures of hindered phenols, unhindered phenols, partially hindered thiobisphenols and diphenylamine, employing a high concentration of free RO2. and coordinated (CoIII)RO2. tert-butyl peroxy radicals generated in the redox-reaction of Co(acac)2 with tert-butyl hydroperoxide. The consecutive H-transfer reactions proceed to equilibrium until the most stable radicals are formed. In this way criteria are obtained for ranking the compared free and coordinated phenoxy radicals according to their relative stabilities. The secondarily generated phenoxy radicals from unhindered phenols after coordination to CoIII are stabilized and cannot take part in further H-transfer reactions.
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  • 100
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    Organic Magnetic Resonance 13 (1980), S. 434-437 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The potential of 13C NMR techniques for studies of nicotine metabolism has been investigated by acquisition and assignment of 13C NMR spectra of nicotine, its metabolites and some related compounds. It is shown that C-2′ of nicotine would be the best site for 13C labelling when using the method to gain further insight into the metabolic pathways of nicotine.
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