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  • 101
    ISSN: 1432-0878
    Keywords: Key words Cytokine ; ELISA ; FACScan ; Lipids ; Macrophage ; Monocyte ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Diabetes (type I and type II) affects approximately 13 million people in the United States. Delayed and incomplete healing of wounds can be a major problem for diabetic patients. Macrophages are an important cell in the complex process of wound repair representing the major source of cytokines throughout the wound-healing process. Cytokines mediate many of the cellular responses critical to timely wound repair. It has been suggested that diabetes impairs wound healing through disruption of local cytokine production. Our previous in vivo studies in rats demonstrated that diabetes-induced and diet-induced hyperlipidemia cause changes in macrophage phenotype and function (Iacopino 1995; Doxey et al. 1998), suggesting that alterations in macrophage cytokine profiles represent the cellular/molecular mechanism responsible for delayed wound healing. The purpose of this study was to investigate how monocyte maturation/differentiation and cytokine production were altered by serum lipids in an in vitro system using human cells. Commercially prepared purified human monocytes were cultured and exposed to serum lipids. Phenotypic analysis of differentiated macrophages was then performed by flow cytometry and fluorescent microscopy using surface antigens specific for various macrophage subsets. Selected cytokines in conditioned medium were assayed using commercial human enzyme-linked immunosorbent assay (ELISA) kits. We demonstrate that serum lipids cause an increase in monocytic differentiation leading to an inflammatory macrophage phenotype rather than a reparative/proliferative phenotype. We also show that serum lipids cause a generalized decrease in macrophage cytokine production using interleukin-1 beta (IL-1β), tumor necrosis factor alpha (TNF-α), platelet-derived growth factor (PDGF), and transforming growth factor beta 1 (TGF-β1) as marker cytokines. Our present in vitro results using human cells confirm our previous in vivo studies in the rat and support the hypothesis that diabetes-induced hyperlipidemia alters the monocyte differentiation process resulting in changes of macrophage subsets and cytokine release at the wound site, ultimately impairing the wound-healing process.
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  • 102
    ISSN: 1432-0878
    Keywords: Key words Cultured epidermis ; Keratinocyte ; Epithelialization ; Wound healing ; Human ; Mouse (NMRI)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  Sheets of cultured allogeneic human keratinocytes have been used for the treatment of burns and chronic leg ulcers but there has been no animal assay for the therapeutic action of these cultures. In order to analyze the effects of frozen cultures of human keratinocytes on wound healing, we have developed such an assay based on the rate of repair of full-thickness skin wounds in immunocompetent NMR1 mice. Reepithelialization of the control wounds, originating from the murine epithelium at the edge of the wound, occurred at a constant rate of advance of 150 µm/day. When frozen cultured human epidermal sheets were thawed at room temperature for 5–10 min and applied to the surface of the wound, the murine epithelium advanced at 267 µm/day. Most wounds treated with frozen cultures completely healed after 10 days, whereas most control wounds required 16 days. The accelerated reepithelialization did not depend on the presence of proliferative human keratinocytes in the frozen cultures. The cultures also promoted early formation of granulation tissue and laminin deposition over the surface of the wound bed. This simple assay should permit quantitative analysis of the effects on healing exerted not only by cultured cells, but also by proteins and small molecules.
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  • 103
    ISSN: 1432-0878
    Keywords: Key words Interleukin-18 ; Hyperosmotic conditions ; Epithelial cells ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  Interleukin-18 is a novel multifunctional cytokine, which enhances natural killer cell activity and promotes the induction of cytokine production, including that of interferon-γ by T cells and antitumor effects. Interleukin-18 is produced by cells of several different tissues (e.g., macrophages, keratinocytes, osteoblasts, and intestinal epithelium); however, it is unclear what physiological conditions or stimuli induce interleukin-18 production. To determine physiological conditions for the production of interleukin-18, we have examined the effect of mannitol-induced hyperosmotic conditions on normal human umbilical vein endothelial cells (HUVEC) and eight established human epithelial-like cell lines (Intestine 407, Caco-2, A253, HeLa, SCC25, HT1197, ACHN, A549). Hyperosmotic conditions induced interleukin-18 immunoreactivity in all the human cell lines tested, as detected by immunocytochemistry. The enhanced interleukin-18 production was also observed when mannitol was replaced with NaCl as the inducer of hyperosmotic stress. Enzyme-linked immunosorbent assays revealed that interleukin-18 concentrations in cell extracts were significantly increased by hyperosmotic conditions. Reporter gene assays also revealed that hyperosmotic conditions stimulated transcriptional activity of the interleukin-18 promoter. These results show for the first time that hyperosmotic stress is a stimulator of interleukin-18 production in epithelial-like cells.
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  • 104
    ISSN: 1432-0878
    Keywords: Key words α1-Microglobulin ; Bikunin ; Inter-α-trypsin inhibitor ; Mast cells ; Trypstatin ; Urinary trypsin inhibitor ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  We recently reported that the rat mast cell proteinase inhibitor trypstatin is genetically identical with the second half of inter-α-trypsin inhibitor light chain (ITI-LC), also known as bikunin or urinary trypsin inhibitor (UTI). In this study, therefore, immunoreactivities of mast cells of various human tissues were examined with three antibodies, anti-human ITI-LC, anti-ITI, which recognizes mainly heavy chains or the sugar moiety of ITI, and anti-α 1-microglobulin (α1mG). ITI-LC immunoreactivity was strongly found in mast cells in the connective tissues of various organs except for those of the propria mucosae of small intestine. Neither anti-ITI antibody nor anti-α1mG antibody reacted with mast cells in various tissues. By reverse transcription-polymerase chain reaction (RT-PCR) analysis, α1mG/ITI-LC mRNA was not detected in the skin and tongue, and only weakly in small intestine, although ITI-LC immunoreactivity was strongly detected in these tissues. Furthermore, the mRNA was not expressed in cultured human mast cells. These results suggest that ITI-LC protein is stored in the granules of human connective tissue mast cells, though is not produced by them.
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  • 105
    ISSN: 1432-0878
    Keywords: Key words Osteoblasts ; Extracellular matrix ; Transforming growth factor-β1 ; Basic fibroblast growth factor ; Apert’s syndrome ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  The phenotype of Apert osteoblasts differs from that of normal osteoblasts in the accumulation of macromolecules in the extracellular matrix. Apert osteoblasts increase type I collagen, fibronectin and glycosaminoglycans secretion compared with normal osteoblasts. Because the extracellular matrix macromolecule accumulation is greatly modulated by transforming growth factor-β1, we examined the ability of normal and Apert osteoblasts to secrete transforming growth factor-β1 by CCL-64 assay and to produce transforming growth factor-β1 by analysis of the mRNA expression of transforming growth factor-β1. Northern blot analysis revealed an increased amount of transforming growth factor-β1 mRNA expression in Apert osteoblasts compared with normal ones. Moreover, the level of the active transforming growth factor-β1 isoform was higher in Apert than in normal media. In pathologic cells, the increase in transforming growth factor-β1 gene expression was associated with a parallel increase in the factor secreted into the medium. The level of transforming growth factor-β1 was decreased by the addition of basic fibroblast growth factor. Transforming growth factor-β1 is controlled temporally and spatially during skeletal tissue development and produces complex stimulatory and inhibitory changes in osteoblast functions. We hypothesise that in vitro differences between normal and Apert osteoblasts may be correlated to different transforming growth factor-β1 cascade patterns, probably due to an altered balance between transforming growth factor-β1 and basic fibroblast growth factor.
    Type of Medium: Electronic Resource
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  • 106
    ISSN: 1432-0878
    Keywords: Key words Endothelin ; Endothelin receptors ; Endothelin-converting enzyme ; Ovary ; In situ hybridization ; Human ; Cynomolgus monkey
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The endothelin system is composed of three endothelin isoforms (ET-1, ET-2, and ET-3), the endothelin receptors ETA and ETB, and the endothelin-converting enzyme (ECE). Besides having a major vasoactive role, endothelins have roles in different cell types at a local level. We investigated the presence of the different components of the endothelin system in primate ovaries. Human ovaries and gonadotropin-stimulated monkey ovaries were studied using immunohistochemistry for endothelin, and in situ hybridization with probes for ET-1, ET-2, ET-3, ETA and ETB receptors, and ECE. ET-1 and ETA receptors were detected in endothelial cells and vascular smooth muscle cells, respectively, in stromal vessels adjacent to follicles and corpora lutea. ETB receptors and ET-1 were found in the endothelial cells of capillaries of corpora lutea. ECE was present in internal theca cells of secondary, de Graaf, atretic follicles, and in luteinized granulosa cells of the corpora lutea. The endothelin system components are present in or around the follicles of human and monkey ovaries. Although the components are not expressed in the same cell types, they are synthesized, mainly in follicles, by cells that are in close proximity. Thus, the endothelin system could act in a paracrine manner. ECE expression in steroid-producing cells changes its compartmentalization during follicle maturation.
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  • 107
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 295 (1999), S. 297-305 
    ISSN: 1432-0878
    Keywords: Key words Trophoblast ; Macrophages ; Placenta ; Cell culture ; Paracrine regulation ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract In view of the accumulating evidence for paracrine mechanisms regulating trophoblast function, we tested the hypothesis that placental macrophages affect trophoblast activity in a paracrine fashion. Trophoblast was isolated from 17 term placentas (–IP). One aliquot of cells was further immunopurified (+IP) using an HLA class I antibody. This increased the proportion of trophoblast (+IP 〉97%; –IP ∼70%) as identified by rigorous immunocytochemistry. Most (∼70%) non-trophoblast cells in –IP were macrophages. The cells were cultured for 5 days with a daily medium change. In addition, +IP cells from seven placentas were cultured with lipopolysaccharide (LPS)-stimulated or -unstimulated macrophage-conditioned media. The concentrations of lactate, trophoblast-specific hormones, human chorionic gonadotropin-β (hCG-β) and human placental lactogen (hPL), of several prostanoids and of endothelin-1 and angiotensin II were determined in the culture media. The accumulated amounts of substances released into the culture media, corrected for the greater proportion of trophoblast in +IP cultures, were on average two- to threefold higher (hCG-β: 18-fold) in +IP than in –IP, with the exception of endothelin-1,2 (no change), angiotensin II (–70%) and 6-keto-prostaglandin-F1α (–40%). [3H]leucine incorporation into the trichloroacetic acid (TCA)-precipitable pool measured on day 5 was twofold higher in +IP than in –IP. Addition of conditioned media reverted these changes. The data demonstrate that placental macrophages in culture affect trophoblast biosynthetic activity in a paracrine fashion. We conclude that macrophages are important regulators of trophoblast activity.
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  • 108
    ISSN: 1432-0878
    Keywords: Key words Cerebrovascular development and injury ; Hemangioma ; Angiogenesis ; Immunocytochemistry ; Adhesion molecules ; Conventional transmission and high-voltage electron microscopy ; Mouse (C57BL ; SJL/J) ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Blood vessels from the vasculature of mouse brains during postnatal development and from human brain tumors (hemangiomas) removed at biopsy were examined immunocytochemically by transmission electron microscopy (TEM) or high-voltage transmission electron microscopy (HVEM) to determine the expression of intercellular adhesion molecule-1 (ICAM-1). In the mouse brains, ICAM-1 was shown to be initially expressed on the luminal and abluminal endothelial cell (EC) surfaces on day 3 after birth. ICAM-1 intensity increased on the luminal EC surfaces and labeled vesiculotubular profiles (VTS, defined in the present report) between days 5 and 7. After 2 weeks and at 6 months after birth, ICAM-1 labeling was weak or absent on the luminal EC surfaces. The hemangiomas presented a strong ICAM-1 reaction product on the luminal EC surfaces of small and large blood vessels associated with the VTS, with a weaker labeling of the abluminal or adventitial aspects of larger blood vessels. TEM of vesiculovacuolar structures (VVOs) within ECs from arteries and veins also demonstrated reaction product for ICAM-1 labeling. Three-dimensional stereo-pair images in the HVEM enhanced the visualization of gold particles that were attached to the inner-delimiting membrane surfaces of EC VTS, and VVOs, respectively. These observations raise the possibility that the neonatal leukocytes and tumor cells may utilize these endothelial structures as a route across the developing and injured blood-brain barrier (BBB).
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  • 109
    ISSN: 1432-0878
    Keywords: Key words Atherosclerosis ; Culture model ; Endothelial cell ; Endothelin-1 ; Oxidized LDL ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract We investigated the structural and functional properties of human umbilical vein endothelial cells (HUVECs) cultured on a two-chamber culture model system using an amnion membrane. Compared to HUVECs cultured on a plastic dish, HUVECs cultured on the model system exhibited several features similar to those of in vivo vessels, including formation of the intercellular junctional devices and expression of tight junction-associated protein ZO-1 and adherence junction-associated protein α-catenin. Furthermore, we found that HUVECs had a property of polar secretion of endothelin-1 (ET-1). About 90% of the total amount of synthesized ET-1 was found in the lower well, designated as the basal side. When HUVECs were incubated with either native low-density lipoproteins (nLDLs) or oxidized LDLs (oxLDLs) at a concentration of 100 μg/ml, ET-1 secretion was significantly increased, dependent on the cell side (apical vs basal) on which the nLDLs or oxLDLs were loaded. When the LDLs were loaded on the apical side, the secretion of ET-1 from HUVECs on the apical side was increased by 48% (nLDL) and 61% (oxLDL), whereas it was accompanied by a concomitant decrease of ET-1 on the basal side (45% by nLDLs and 38% by oxLDLs). When loaded on the basal side, however, ET-1 was increased by 23% (nLDLs) and 53% (oxLDLs) on the basal side, with a 26% simultaneous decrease of ET-1 on the opposite side for both nLDLs and oxLDLs. On the contrary, high-density lipoproteins (HDLs) inhibited ET-1 secretion from HUVECs on the opposite side of the well on which HDLs were loaded; there was a 57% decrease on the basal side when HDLs were loaded on the apical side, and a 46% decrease on the apical side when loaded on the basal side. These results indicate that modulation of ET-1 secretion from ECs by lipoproteins is virtually dependent on the place (apical vs basal) where these proteins are present. The finding that nLDLs and oxLDLs enhance ET-1 secretion by ECs in a polarized pattern suggests that ET-1 may be involved in pathophysiological processes such as atherogenesis.
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  • 110
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 295 (1999), S. 151-158 
    ISSN: 1432-0878
    Keywords: Key words Class II MHC-positive cells ; Human leukocyte antigen-DR ; Dental pulp ; Dendritic cells ; Macrophages ; Ultrastructure ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The distribution and ultrastructure of class II major histocompatibility complex (MHC)-positive cells were investigated in human dental pulp, employing immunohistochemistry using an anti-human leukocyte antigen (HLA)-DR-monoclonal antibody. HLA-DR-immunopositive cells, appearing spindle-like or dendritic in profile, were densely distributed throughout the dental pulp. Under the electron microscope, these cells exhibited various sizes of vesicles containing clear or opaque contents, multivesicular bodies and characteristic fine tubulovesicular structures in their cytoplasm. Some reactive cells possessed coated pits and vesicles including electron-dense materials, indicating an active endocytosis. At the periphery of the pulp tissue, the HLA-DR-immunopositive cells were predominantly situated in the subodontoblastic layer, with some located in the odontoblast layer and/or predentin and extending their cytoplasmic processes into the dentinal tubules. Cell processes of these cells occasionally made contact with several odontoblast processes in the same way as the nerve fibers in the predentin. These cells never contained the typical phagosomes frequently observed in the HLA-DR-immunoreactive macrophages in the subodontoblastic layer and the pulp core. The results suggest that the HLA-DR-immunopositive cells in the odontoblast layer and/or predentin have some regulatory function on the odontoblasts under physiological conditions, in addition to their involvement in the initial defense reaction after tooth injury.
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  • 111
    ISSN: 1615-6102
    Keywords: Cumulus oophorus ; Ovarian follicle ; Fertilization ; Ultrastructure ; Immunocytochemistry ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The fine structure of the human cumulus oophorus has been reviewed on the basis of scanning and transmission electron microscopic observations as well as of immunofluorescence data. Tissues sampled from preovulatory ovarian follicles and cumulus-enclosed oocytes and fertilized eggs (collected from the oviduct or obtained during in vitro fertilization procedures) have been evaluated from a microtopographic and morphodynamic point of view in order to better clarify the possible role of this population of cells. In particular, the following aspects have been studied and discussed: the presence of multiple close contacts (modulated by the interposition of the zona pellucida) between the oocyte surface and the long microvillous evaginations projecting from the inner aspect of corona cells surface (through these structures the intraovarian cumulus oophorus may control oocyte growth and metabolism up until the time of ovulation); the occurrence of different subpopulations of cells (steroid-synthetic cells, cells producing adhesive proteins, leukocytes, macrophages) in the postovulatory, extraovarian cumulus oophorus surrounding oocytes, zygotes and early developing embryos. All these elements found in the cumulus mass may positively act, through their paracrine activities, on the chemical composition of the microenvironment in which fertilization occurs.
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  • 112
    ISSN: 1615-2573
    Keywords: Smooth muscle cell ; Heterogeneity ; Coronary artery ; Human ; Immunohistochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The arterial media is composed of a heterogeneous population of smooth muscle cells (SMCs). Recently, the properties of SMCs were observed to be heterogeneous not only among individual cells but also among arteries of the same vascular bed. To test the hypothesis that a site-specific heterogeneity exists in the SMCs of human coronary arteries, we examined the expression of desmin, vimentin, calponin, and high-molecular-weight (h-) caldesmon in arteries of various sizes. Specimens of arteries were obtained at autopsy from 12 patients: 6 adults (67 ± 4 years old); 3 younger adults (26 ± 2 years old); and 3 neonates. The size of the arteries was estimated by the number of SMC layers of the media. The expression was compared in SMCs of large arteries (〉10 layers in adults, 〉5 layers in neonates), medium-sized arteries (5–10 layers in adults, 3–5 SMC layers in neonates), and small arteries (〈3 layers). In adults, the percentage of arteries positive for desmin was lower in the small (17% ± 3%) and medium-sized arteries (44% ± 12%) than in the large arteries (94% ± 6%) (P 〈 0.01). The percentage of arteries positive for calponin was also lower in the small (18% ± 2%) and medium-sized arteries (66% ± 5%) than in the large arteries (100%) (P 〈 0.01). The percentage for vimentin and h-caldesmon did not differ among large, medium-sized, and small arteries. These observations in adults were similar to those in younger adults or neonates. The phenotypes of medial SMCs are vessel sizedependent in human coronary arteries. This finding should be important for understanding the site-specific characteristics of vascular function in the regulation of myocardial perfusion or those of vascular responses to environmental changes.
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  • 113
    Electronic Resource
    Electronic Resource
    Springer
    European journal of applied physiology 80 (1999), S. 386-393 
    ISSN: 1439-6327
    Keywords: Key words Skeletal Muscle ; Human ; Force/velocity ; Fatigue ; Isokinetic testing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The purpose of the study was to obtain force/velocity relationships for electrically stimulated (80 Hz) human adductor pollicis muscle (n = 6) and to quantify the effects of fatigue. There are two major problems of studying human muscle in situ; the first is the contribution of the series elastic component, and the second is a loss of force consequent upon the extent of loaded shortening. These problems were tackled in two ways. Records obtained from isokinetic releases from maximal isometric tetani showed a late linear phase of force decline, and this was extrapolated back to the time of release to obtain measures of instantaneous force. This method gave usable data up to velocities of shortening equivalent to approximately one-third of maximal velocity. An alternative procedure (short activation, SA) allowed the muscle to begin shortening when isometric force reached a value that could be sustained during shortening (essentially an isotonic protocol). At low velocities both protocols gave very similar data (r 2 = 0.96), but for high velocities only the SA procedure could be used. Results obtained using the SA protocol in fresh muscle were compared to those for muscle that had been fatigued by 25 s of ischaemic isometric contractions, induced by electrical stimulation at the ulnar nerve. Fatigue resulted in a decrease of isometric force [to 69 (3)%], an increase in half-relaxation time [to 431 (10)%], and decreases in maximal shortening velocity [to 77 (8)%] and power [to 42 (5)%]. These are the first data for human skeletal muscle to show convincingly that during acute fatigue, power is reduced as a consequence of both the loss of force and slowing of the contractile speed.
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  • 114
    Electronic Resource
    Electronic Resource
    Springer
    European journal of applied physiology 79 (1999), S. 347-352 
    ISSN: 1439-6327
    Keywords: Key words Citrate synthase activity ; Human ; Myoglobin concentration ; Protocols ; Resistance training ; Vastus lateralis muscle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The aim of this study was to determine the effects of 8 weeks of resistance training (RT) on the myoglobin concentration ([Mb]) in human skeletal muscle, and to compare the change in the [Mb] in two different RT protocols. The two types of protocol used were interval RT (IRT) of moderate to low intensity with a high number of repetitions and a short recovery time, and repetition RT (RRT) of high intensity with a low number of repetitions and a long recovery time. A group of 11 healthy male adults voluntarily participated in this study and were divided into IRT (n = 6) and RRT (n = 5) groups. Both training protocols were carried out twice a week for 8 weeks. At the completion of the training period, the one-repetition maximal force values and isometric force were increased significantly in all the subjects, by about 38.8% and 26.0%, respectively (P 〈 0.01). The muscle fibre composition was unchanged by the 8 weeks of training. The muscle fibre cross-sectional areas were increased significantly by both types of training in all fibre types (I, IIa and IIb, mean +16.1%, P 〈 0.05). The [Mb] showed no significant changes at the completion of the training [IRT from 4.63 (SD 0.63) to 4.48 (SD 0.72), RRT from 4.47 (SD 0.75) to 4.24 (SD 0.80) mg · g−1 wet tissue] despite a significant decrease in citrate synthase activity [IRT from 5.27 (SD 1.45) to 4.49 (SD 1.48), RRT from 5.33 (SD 2.09) to 4.85 (SD 1.87) μmol · min−1 · g−1 wet tissue; P 〈 0.05] observed after both protocols. These results suggested that myoglobin and mitochondria enzymes were regulated by different mechanisms in response to either type of RT. Moreover, the maintained [Mb] in hypertrophied muscle should preserve oxygen transport from capillaries to mitochondria even when diffusion distance is increased.
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  • 115
    ISSN: 1439-6327
    Keywords: Key words Fatigue ; Movement ; Position ; Muscle ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We have tested the hypothesis that agonist and antagonist muscle fatigue could affect the final position of rapid, discrete movements. Six subjects performed consecutive elbow flexion and extension movements between two targets, with their eyes closed prior to, and after fatiguing the elbow extensor muscles. The results demonstrate that elbow extension movements performed in the post-test period systematically undershot the final position as compared to pre-test movements. However, attainment of the aimed final position in elbow flexion movements was unaffected by fatiguing of the extensor muscles. Undershoot of the final position obtained in extension movements was associated with agonist muscle fatigue, a result that was expected from the point of view of current motor control theories, and that could be explained by a reduced ability of the shortening muscle to exert force. On the other hand, the absence of the expected overshoot of the final position when the antagonist is fatigued, indicates the involvement of various reflex and/or central mechanisms operating around the stretched muscle that could contribute to returning the limb to the standard final position after a brief prominent overshoot.
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  • 116
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    European archives of oto-rhino-laryngology and head & neck 256 (1999), S. 370-372 
    ISSN: 1434-4726
    Keywords: Key words Gastroesophageal reflux disease ; Human ; papilloma virus ; Laryngeal papillomatosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The hallmark of gastroesophageal reflux disease (GERD) is an increased exposure of esophageal and laryngeal mucosa to gastric juice. This exposure can cause complications such as chronic laryngitis or chronic respiratory diseases. We report our experience in managing three pediatric patients with severe recurrent juvenile laryngeal papillomatosis (JLP) associated with GERD. All patients showed a high rate of recurrence requiring multiple laser surgeries. Systemic αinterferon therapy over a period of more than 1 year and photodynamic therapy with dihematoporphyrin produced no improvement. However, after therapy for GERD, the rate of recurrence of JLP decreased significantly. Although the course of respiratory papillomatosis is known to fluctuate, our findings suggest that gastroesophageal reflux may have a role in aggravating papillomatosis.
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  • 117
    ISSN: 1573-6792
    Keywords: EEG ; Alpha activity ; Spatial segmentation techniques ; Wakefulness ; Sleep onset ; REM sleep ; Dream imagery ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Spontaneous alpha activity clearly present in relaxed wakefulness with closed eyes, drowsiness period at sleep onset, and REM sleep was studied with spatial segmentation methods in order to determine if the brain activation state would be modulating the alpha spatial microstates composition and duration. These methods of spatial segmentation show some advantages: i) they extract topographic descriptors independent of the chosen reference (reference-free methods), and ii) they achieve spatial data reduction that are more data-driven than dipole source analysis. The results obtained with this study revealed that alpha activity presented a different spatio-temporal pattern of brain electric fields in each arousal state used in this study. These differences were reflected in a) the mean duration of alpha microstates (longer in relaxed wakefulness than in drowsy period and REM sleep), b) the number of brain microstates contained in one second (drowsiness showed more different microstates than did relaxed wakefulness and REM state), and c) the number of different classes (more abundant in drowsiness than in the rest of brain states). If we assume that longer segments of stable brain activity imply a lesser amount of different information to process (as reflected by a higher stability of the brain generator), whereas shorter segments imply a higher number of brain microstates caused by more different steps of information processing, it is possible that the alpha activity appearing in the sleep onset period could be indexing the hypnagogic imagery self-generated by the sleeping brain, and a phasic event in the case of REM sleep. Probably, REM-alpha bursts are associated with a brain microstate change (such as sleep spindles), as demonstrated by its phasic intrusion in a desynchronized background of brain activity. On the other hand, alpha rhythm could be the “baseline” of brain activity when the sensory inputs are minimum and the state is relaxed wakefulness.
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  • 118
    ISSN: 1573-6792
    Keywords: Magnetoencephalography ; Human ; Words ; Tones ; Cerebral dominance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The magnetic flux normal to the scalp surface was measured with a whole-head neuromagnetometer while right-handed subjects (N = 15) were engaged in either an auditory word- or a tone-recognition task. Sources of the recorded magnetic fields were modeled as equivalent current dipoles at 4 ms intervals and the number of sources in the later portion of the magnetic response was used as an index of the degree of brain activation. Significantly more sources were found in the left as compared to the right hemisphere in the word but not the tone task on a group basis. On an individual basis, 13/15 subjects had more sources in the left as compared to the right hemisphere during the word task, while in the tone task 3/10 subjects showed this pattern. Sources of activity were found in the left superior and middle temporal gyri in all subjects with available MRI scans. Sources were also found in the supramarginal gyrus and in medial temporal areas, including the hippocampus, in the majority of cases. MEG appears to be a promising tool for detecting activity in cerebral areas specialized for language and memory function.
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  • 119
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    Plant foods for human nutrition 53 (1999), S. 359-365 
    ISSN: 1573-9104
    Keywords: Consumed ; Different levels ; Fenugreek seeds (Trigonella foenum graecum) ; Germinated ; HDL ; Human ; Hypocholesterolemia ; LDL ; Triglycerides ; VLDL
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effect of consumption of germinated fenugreek seed powder at two different levels, i.e., 12.5 g and 18.0 g on the blood lipid profiles of twenty hypocholesterolemic adults of both sexes in the age range of 50–65 years was studied. The subjects were divided into two groups, i.e., Group I and Group II who were asked to incorporate the powder into any dish of their choice at the rates of one packet per day containing 12.5 g and 18.0 g of the germinated powder, respectively, for a period of one month. Fasting blood was drawn intravenously one day before and at the end of 30 days feeding trials. The findings revealed that germination had brought distinct changes in soluble fiber content of the seeds. Consumption of the seed at both the levels resulted in a hypocholesterolemic effect. Between the two levels, higher levels of consumption, i.e., 18.0 g of the germinated seed resulted in a significant reduction in total cholesterol and LDL levels. No significant changes were found in HDL, VLDL and triglyceride levels in all the subjects.
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  • 120
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    Calcified tissue international 7 (1971), S. 175-190 
    ISSN: 1432-0827
    Keywords: Bone ; Human ; Age ; Glycosaminoglycans
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les glycosaminoglycanes de l'os humain compact du fémur sont identifiés et leur concentration et distribution sont déterminées à partir de cas d'autopsie, d'âges variables, allant du nouveau-né à des sujets de 94 ans. L'absence d'altérations post-mortem des glycosaminoglycanes osseux est déterminée au niveau de l'os fémoral de chien, au bout de 72 heures. Le chondroitine-4-sulfate constitue le glycosaminoglycane majeur de l'os humain: de plus, une fraction mineure semble être constituée par l'acide hyaluronique. Les proportions de glycosaminoglycanes varient inversement en fonction, de l'âge chez des sujets en pleine croissance: mais aucun changement n'est observé plus tardivement. La distribution des glycosaminoglycanes est identique chez les sujets adultes. Seules de faibles différences, concernant cette distribution, sont relevées. Chez les sujets jeunes elles sont, peut-être, liées à des changements de poids moléculaire peu élevés ou au sulfate chondroitine sulfaté, peu élevé et, chez un sujet vieil à une proportion plus grande d'acide hyaluronique.
    Abstract: Zusammenfassung Die Glykosaminoglykane aus menschlicher Compacta des Oberschenkels wurden charakterisiert und ihre Konzentrationen und Muster an Autopsien von Menschen verschiedenen Alters (Neugeborene bis 94jährige) festgelegt. Fällungen mit Cetylpyridin und Fraktionierungsmethoden wurden angewendet. Am Hundefemur konnte festgestellt werden, daß sich das Glykosaminoglykanmuster im Knochen bis zu 72 Std post mortem nicht veränderte. Als wichtigstes Glykosaminoglykan des menschlichen Knochens wurde das Chondroitin-4-sulfat identifiziert; dazu wurde ein kleiner Anteil versuchsweise als Hyaluronsäure eingestuft. Die Konzentrationen der Glykosaminoglykane standen in umgekehrtem Verhältnis zum Alter des im Wachstum stehenden Menschen, jedoch wurde nach dessen Abschluß keine Veränderung mehr beobachtet. Das Glykosaminoglykanmuster sieht für alle erwachsenen Menschen ähnlich aus. Nur kleine Abweichungen von diesem Muster konnten bei jungen Menschen festgestellt werden; möglicherweise sind sie auf eine leichte Änderung im Molekulargewicht oder auf eine schwache Sulfatierung des Chondroitinsulfates zurückzuführen. Dies gilt ebenso für einen alten Menschen, dessen Knochen einen höheren Anteil an Hyaluronsäure aufweisen.
    Notes: Abstract Glycosaminoglycans from human femoral compact bone were characterized and their concentrations and patterns were determined in autopsy cases of various ages, newborn to 94 years of age. Cetylpyridinium precipitation and fractionation methods were used. Absence of postmortem changes of bone glycosaminoglycan pattern for as long as 72 hours was checked on dog femoral bone. Chondroitin-4-sulphate was identified as the predominating glycosaminoglycan of human bone; in addition a minor part was tentatively identified as hyaluronic acid. Concentrations, of glycosaminoglycans were inversely related to age in growing subjects, but no change was noted later in life. The glycosaminoglycan pattern had a similar appearance for all of the adult subjects. Only small deviations from this pattern had a similar for young subjects, possibly due to low molecular weight change or low sulphated chondroitin sulphate; and for one old subjects to a higher proportion of hyaluronic acid.
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  • 121
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    Psychopharmacology 19 (1971), S. 207-223 
    ISSN: 1432-2072
    Keywords: Chlorpromazine ; Non-Polar Metabolites ; Radiolabeled Derivative Formation ; Plasma Extracts ; Dog ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Conditions have been established for the quantitative formation of radiolabeled derivatives of chlorpromazine, chlorpromazine sulfoxide and their demethylated analogs in plasma extracts. Tritiated N-acetyl derivatives are formed from the demethylated compounds and C14-quaternary amines from the tertiary amines by acetylation and methylation, respectively. These reactions are quantitative over a wide range of concentrations. The reactions may be performed sequentially when chloropromazine and its Nor derivatives (or chlorpromazine sulfoxide and its Nor derivatives) exist in a single extract. Herein, the mixture is first acetylated and subsequently methylated. The labeled derivatives are quantitatively separated and recovered by selective solvent partition. An extraction procedure has been suggested by which chlorpromazine and its Nors may be separated from chlorpromazine sulfoxide and its Nor derivatives so that each fraction may be subjected to the sequential acetylation and methylation reactions. Recoveries of μg quantities of standards from plasma are less than quantitative, probably because of losses due to glass adsorption and protein binding, but may be corrected with appropriate internal standards. As low as 15–20 ng/ml of each compound are measurable in a 3 ml plasma aliquot. The method has been applied to a limited number in vivo experiments in dogs and in humans.
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  • 122
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    Cell & tissue research 121 (1971), S. 358-376 
    ISSN: 1432-0878
    Keywords: Leukocyte ; Peripheral ; Human ; Ultrastructure ; Osmium-Zinc-Impregnation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Leukozytenkonzentrate des peripheren Blutes von gesunden Versuchs-personen wurden in 2,5%iger Glutaraldehyd-Lösung (0,1 M Na-Cacodylat-Puffer, pH 7,3) vorfixiert und nach der Methode von Maillet (1959) mit OsO4 + ZnJ2 inkubiert. Dickschnitte wurden mit dem Mikroanalysator (Siemens) auf ihren Gehalt an Osmium, Zink und Jod analysiert und die Dünnschnitte mit dem Elektronenmikroskop untersucht. Bei der Mikroanalyse ließen sich Osmium und Zink, nicht aber Jod nachweisen. Die elektronenmikroskopischen Untersuchungen ergaben folgende Resultate: Beträgt der pH-Wert der Inkubationslösung 5,6, so findet sich eine starke Os/Zn-Imprägnation des Golgi-Apparates, des Kernspaltes und des Endoplasmatischen Retikulums bei sämtlichen Arten der weißen Blutzellen. Die Matrix der Mitochondrien dieser Zellen ist im allgemeinen weniger stark imprägniert. Auch in den Lysosomen der Monozyten und Plasmazellen sind geringfügige Os/Zn-Präzipitate nachweisbar. Es findet keine Reaktion in den Leukozytengranula und in den Zentriolen statt. Dagegen zeigen die Lipidtropfen der eosinophilen Granulozyten eine sehr starke, homogene Os/Zn-Imprägnation. Diese ist bereits nach 40 min Inkubation voll ausgeprägt. Bei einer Schnittkontrastierung mit Uranylacetat werden die Os/Zn-Präzipitate wieder herausgelöst, wenn die Kontrastierung länger als 2 min dauert. Eine Bleikontrastierung hat keinen Einfluß auf die Os/Zn-Präzipitate. Bei Erhöhung des pH-Wertes der Inkubationslösung auf 6,2 kommt es zur starken Imprägnation des Externums der eosinophilen Granula, während Kernspalt, Golgi-Apparat und Mitochondrienmatrix keine Reaktion zeigen. Die Imprägnationsdichte der Lipidtropfen der eosinophilen Granulozyten ist pH-unabhängig.
    Notes: Summary “Buffy coats” of normal human peripheral blood were fixed in 2.5% glutaraldehyde (buffered with 0.1 M Na-cacodylate, pH 7.3) and incubated with a mixture of osmium tetroxide and zinc iodide (pH 5.2) after the method of Maillet (1959). Utilizing an electron probe microanalyser (Siemens), the authors demonstrated the presence of osmium and zinc in the specimen, whereas the presence of iodide could not be proved with certainty. The ratio of osmium and zinc in the precipitates ranges from 3/2 to 4/1. Electron microscopic studies of the leukocytes have lead to the following results: the Golgi apparatus, the perinuclear cleft and the endoplasmic reticulum (ER) of all types of leukocytes are strongly impregnated with osmium/zinc, whereas the matrices of the mitochondria are less impregnated. Osmium/zinc precipitates have also been detected in the lysosomes of monocytes and plasma cells. No reaction was evident in the leukocytic granules or centrioles. The presence of lipid droplets in eosinophils has been demonstrated. These droplets show a dense homogeneous osmium/zinc impregnation which reaches its maximum after 40 minutes of incubation, compared with much longer incubation times (5–6 hours) for other cellular components. Setting the pH of the osmium tetroxide-zinc iodide solution to 6.2 resulted in a dense impregnation of the “externum” of the eosinophilic granules. At this same pH, the perinuclear cleft, Golgi apparatus and mitochondrial matrix did not show a definite reaction. The extent of impregnation of the lipid droplets of the eosinophils showed no dependency on pH. Care must be taken when a stain containing uranyl acetate is used since this substance dissolves the Os/Zn precipitates. Exposure of the precipitates to the uranyl acetate for longer than 2 minutes results in gradual dissolution within complete dissolution in 10 minutes.
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  • 123
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    Cell & tissue research 122 (1971), S. 145-159 
    ISSN: 1432-0878
    Keywords: Brain stem ; Human ; Nucleus reticularis lateralis ; Lipofuscin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Die Gestalt des Nucleus reticularis lateralis, des Nucleus interfascicularis hypoglossi, des Kerns von Roller und einer bisher unbekannten Zellschicht (Repagulum cuneati) wird beschrieben. Dafür werden Serien von 800 μ dicken, mit Aldehydfuchsin gefärbten Schnitten herangezogen. Durch diese Methode werden die in den Nervenzellen enthaltenen Lipofuscinkörnchen elektiv dargestellt. Die stereomikroskopischeUntersuchung aufgehellter Schnitte kann zeitraubende Rekonstruktionen ersetzen. Der Nucleus reticularis lateralis wird in neun regelmäßig angelegte Areale unterteilt: Pars principalis, dorsalis, medialis, lateralis, perivagalis, marginalis disseminata und subtrigeminalis, sowie Promontorium und Repagulum cuneati. Zusammen mit dem Nucleus interfascicularis hypoglossi und dem Kern von Roller tragen die Unterkerne des Nucleus reticularis lateralis zahlreiche gemeinsame Züge, so daß sie als eine morphologisch und wahrscheinlich auch funktionell zusammengehörige Gruppe beschrieben werden können. Die Studie weicht in der Nomenklatur und den Abgrenzungen der einzelnen Areale in zahlreichen Einzelheiten von den Darstellungen anderer Autoren ab. Diese Unterschiede werden diskutiert.
    Notes: Summary The three dimensional shape of the nucleus reticularis lateralis, nucleus interfascicularis hypoglossi, the nucleus of Roller and a hitherto unknown cellular layer (Repagulum cuneati) is described on the basis of 800 μ sections, which are stained with aldehydefuchsin. By this method lipofuscin granules in the nerve cells are stained selectively. The stereomicroscopical investigation of the sections can replace time consuming reconstructions. The nucleus reticularis lateralis is divided into nine constantly occuring areas: pars principalis, dorsalis, medialis, lateralis, perivagalis, marginalis disseminata and subtrigeminalis, promontorium and repagulum cuneati. Together with the nucleus interfascicularis hypoglossi and the nucleus of Roller the subnuclei of the nucleus reticularis lateralis have many features in common indicating them to represent a morphological and presumably a functional unit. The present study is at variance in numerous details with the conceptions of other authors concerning the nomenclature and delineation of the nuclei. These differences are discussed.
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  • 124
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    Cell & tissue research 113 (1971), S. 322-343 
    ISSN: 1432-0878
    Keywords: Exocrine pancreas ; Human ; Release mechanism ; Cilia ; Junctional complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung 1. An der exokrinen Pankreaszelle des Menschen lassen sich eine Basalzone (ER, Zellkern), eine Golgi-Zone und ein apikaler Zellpol unterscheiden. Die Zymogengranula entstehen durch Membranabknospung aus dem Golgi-Apparat und werden am apikalen Zellpol gespeichert. Die Lumenseite der exokrinen Zelle ist von dichtstehenden Mikrovilli besetzt (200–300 pro Zelloberfläche), die eine netzig-fibrilläre Längsstruktur zeigen. 2. Als morphologisches Substrat für den Vorgang der Extrusion werden wenige elektronendichte Granula am apikalen Pol beschrieben, die durch Aneinanderlagerung und Verschmelzung der Hüllmembranen Doppelformen von Granula oder kurze Granulaketten bilden. Die Extrusion wird abgeschlossen durch das Verschmelzen der Hüllmembran der einzelnen oder komplexen Granula mit der Plasmamembran, durch Ausbildung einer Öffnung in der Plasmamembran und durch das Ausfließen des Granuluminhaltes. Die Zelloberfläche von exokrinen Zellen mit lebhafter Extrusion zeigt nur spärlichen Besatz mit Mikrovilli. 3. Die exokrinen Zellen innerhalb eines Azinus werden an den apikalen und seitlichen Kontaktflächen durch ein differenziertes Schlußleistennetz (Zonulae occludentes, Z. adhaerentes, Desmosomen) verbunden, Tonofibrillen verlaufen bogenförmig von einer Verschlußzone zur nächsten und strahlen radiär ins Zytoplasma der exokrinen Zellen aus. 4. Die Epithelzellen der Schaltstücke sind durch ähnlich gebaute Haftzonen mit den exokrinen Zellen und untereinander verbunden; ihr Zytoplasma enthält einen kleinen Golgi-Apparat und regelmäßig langgestreckte Zilien (9+2-Muster), die aus einer trichterförmigen Vertiefung der Zelloberfläche entspringen und weit in das Schaltstücklumen hineinragen.
    Notes: Summary 1. The cytoplasm of human exocrine pancreatic cells may be divided into 3 regions: basal (ER, nucleus), Golgi zone and apical pole. The zymogen granules are condensed in the Golgi region and are stored at the apical pole. From the surface of a single exocrine cell 200 to 300 microvilli project into the lumen of the acinus, they contain an internal fibrillar structure oriented in the long-axis of each microvillus. 2. Before being released into the lumen of the acinus the content of zymogen granules becomes electron translucent and the limiting membranes of adjacent granules fuse to form duplex or short interconnected series of granules. The release is terminated by coalescence of the limiting membrane of single or complex granules with the plasmalemma, formation of an opening at the cell surface and extrusion of secretory material. Cells with signs of active release have only few microvilli on their luminal surface. 3. In a single acinus the apical and lateral surfaces of exocrine cells are connected by elaborate junctional complexes (zonulae occludentes, z. adhaerentes, desmosomes), in the adjacent cytoplasm curved bundles of tonofilaments run from one junctional complex to the other and extend also over a long distance into the cytoplasm. 4. The epithelial cells of the intercalated ducts are connected with the exocrine cells by the same pattern of junctional complexes and tonofilaments. Their cytoplasm contains a small Golgi complex and always a single cilium, which extends through a funnelshaped indentation of the cell surface over a long distance (6 to 8 μ) into the lumen of the intercalated duct.
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    Cell & tissue research 115 (1971), S. 114-136 
    ISSN: 1432-0878
    Keywords: Germinal centers ; Tonsils ; Human ; Acid phosphatase ; Electronmicroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Mit der von Barka und Anderson (1963) angegebenen Methode wurde elektronenhistochemisch die saure Phosphatase (s. P.) in Keimzentren der menschlichen Tonsille untersucht. Nach mannigfaltigen Abwandlungen der Methode wurden diejenigen Versuchsbedingungen ermittelt, die zu optimalen Reaktionen bei noch genügender Strukturerhaltung führen. Zytoplasmakörper mit s. P.-Reaktion (Lysosomen) ließen sich in sämtlichen Zellarten des Keimzentrums nachweisen. Besonders starke Reaktion wiesen die Phagolysosomen der phagozytierenden Retikulumzellen (Makrophagen) auf. Eindeutige Reaktion war bei pH 5,5–6,0 auch im ER der Germinoblasten, basophilen Stammzellen, Plasmazellen, dendritischen (nichtphagozytierenden) Retikulumzellen und phagozytierenden Retikulumzellen zu finden. Bei pH 6,0 fand sich s. P.-Aktivität an der Außenfläche der Zytomembran von dendritischen Retikulumzellen. Diese Enzymreaktion fiel besonders stark in den Membraneinbuchtungen aus. Sie war auch in dem elektronendichten Material nachweisbar, das die Ausläufer der dendritischen Retikulumzellen häufig umgibt. Diese extrazelluläre Enzymaktivität dürfte in Zusammenhang mit der Anlagerung von Antigenen und Antikörpern an die Zelloberfläche der dendritischen Retikulumzellen stehen.
    Notes: Summary The activity of acid phosphatase has been localized with the aid of the electron microscope in germinal centers of human tonsils according to the method of Barka and Anderson (1963). In order to determine the optimal conditions for fixation and incubation with respect to the maintenance of structural integrity and degree of reaction, several modifications of the method were undertaken. Cytoplasmic bodies with reaction products (lysosomes) could be demonstrated within all cell types of germinal centers. The acid phosphatase reaction in the phagolysosomes of phagocytic reticulum cells (macrophages) was extremly strong. At pH 5.5–6.0, definite reactions were also found in the ER of germinoblasts, germinocytes, basophilic stem cells, plasma cells, dendritic (nonphagocytic) reticulum cells, and phagocytic reticulum cells (macrophages). At pH 6.0 acid phosphatase activity was deposited outside dendritic reticulum cells, i.e. on the surface of their cytomembranes. Within the infoldings of their cytomembrane reaction products were also prominent. The enzyme activity could also be shown in the electron dense material which usually surrounds the branches of the dendritic reticulum cells. The activity of acid phosphatase which appears in the extracellular spaces, may have relation to antigens and antibodies which are attached to the cell surface of the dendritic reticulum cells.
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    Cell & tissue research 115 (1971), S. 461-472 
    ISSN: 1432-0878
    Keywords: Seminiferous Epithelium ; Human ; Germinal cells ; Testis ; Male reproduction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Two variants of a method for determining the quantitative structure of the human seminiferous epithelium are described. Both versions (counting cells in whole tubules and in CA's) utilize specific criteria for the identification of cells, tubules and /or CA's. Both methods utilize the Sertoli cell as a constant with the cell types expressed as numbers of cells per Sertoli cell. One hundred biopsies were quantitated by the tubular method and 100 by the CA method. Counts were found to be reproducible and consistent. Comparisons were made between the two methods, different individuals doing the quantitation, quantitations of the right and left testes of the same subject and between biopsies from the same subject taken at different times. No difference was found between the right and left testes or biopsies from the same subject taken at different times. Quantitation of biopsies from one individual before and after testicular X-ray irradiation show how the method can be applied.
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    Cell & tissue research 122 (1971), S. 479-487 
    ISSN: 1432-0878
    Keywords: Corpus luteum ; Human ; Vacuoles ; Involution ; Autophagy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary A description of the atretic human corpus luteum is given. Membrane-limited bodies of varying dimensions, some containing membrane-whorls, are found in the cytoplasm. These bodies are sometimes limited by a double membrane and reaction product for acid phosphatase is observed both between the double membrane and inside these bodies. The plasma membrane projections penetrating the cell at multiple sites are ATP-ase positive. Our results favour the hypothesis that the plasma membrane is involved in the formation of the limiting membrane around autophagic vacuoles. The process of autophagy is discussed in the light of the cellular energy balance and the possible origin of the hydrolytic enzymes involved in the formation of autophagic vacuoles is given.
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    Cell & tissue research 119 (1971), S. 434-450 
    ISSN: 1432-0878
    Keywords: Epidermis ; Human ; Nuclei ; Age dependent changes ; Cytophotometry ; Karyometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Die Bauchhaut von 23 männlichen Versuchspersonen verschiedener Altersgruppen wurde histologisch, histochemisch und karyometrisch untersucht. Mit drei voneinander unabhängigen Methoden (Gallocyaninchromalaun-, Feulgen- und UV-Methode) wurden die mittlere Nukleinsäuremenge und das Volumen der epidermalen Zellkerne bestimmt. Auf diese Weise wurden etwa 6000 Zellkerne photometrisch und karyometrisch gemessen und die Ergebnisse statistisch ausgewertet. Die ermittelten Werte stellen einen Beitrag zur biorheutischen Metamorphose der menschlichen Epidermis dar. Folgende Befunde wurden erhoben. 1. Bei männlichen Individuen über 64 Jahren kommt es zu einer Abnahme der Zellkernvolumina und des mittleren Nukleinsäuregehaltes um ca. 35%. Gleiche Verhältnisse ergeben sich für die Zellkerne von der letzten Reihe des Stratum spinosum im Vergleich zu Zellkernen des Stratum basale in jeder Altersgruppe. Auch hier nehmen die Nukleinsäuremenge und die Kernvolumina um 35% ab. Die Konzentration der Nukleinsäure bleibt im wesentlichen konstant. 2. Zwischen Nukleinsäuremenge und den Kernvolumina der Epidermiszellen besteht eine lineare Korrelation. Diese läßt sich in Form stochastischer Punktionen unter Angaben der Korrelationskoeffizienten ausdrücken. 3. Durch die Bestimmung von Normalwerten und deren biologischer wie auch altersabhängiger Variationen sind quantitative Abgrenzungen gegen pathologische Befunde möglich.
    Notes: Summary The abdominal epidermis of 23 male humans in different age groups was histologically, histochemically and karyometrically examined. This was done using Gallocyaninchromalum, Feulgen and UV methods in order to determine the average nucleic acid content and the volume of the epidermal cell nuclei. 6000 cell nuclei were examined photometrically and karyometrically and the results were statistically evaluated. The data obtained could contribute to the knowledge of age dependent changes. The results are as follows: 1. In male individuals over 65 years of age, there is a reduction of nuclear volume and of the average nucleic acid content of approximately 35%. There also exists a reduction in the nuclear volume and the nucleic acid content from the cells of the stratum basale to the cells of the stratum spinosum of approximately 35% in each age group. The concentration of nucleic acid is for all practical purposes constant. 2. There is a linear correlation between the amount of nucleic acid and the nuclear volume of epidermal cells. This correlation can be calculated in the form of a stochastic function. The latter is defined by calculating its coefficients. 3. Knowing the normal values and their biological and age-dependent variations it is possible to differentiate between normal and pathological findings.
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 99-107 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polarography of Nickel (II) in the presence of DL-tryptophan has been studied in KNO3 supporting electrolyte. Nickel yields two irreversible steps which are due to the formation of two varieties of complex in sluggish equilibrium with each other. The reduction is an irreversible, kinetically controlled process as evidenced from cyclic voltammetry and i-t curves. Rate constants of the processes are evaluated. The effect of temperature is described.
    Additional Material: 4 Ill.
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 108-114 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch potentiometrische bzw. photometrische pH-Titration wurden Protonierungskonstanten von 1-substituierten Butandion-(2,3)monoximen (1 und 2) und -dioximen (3) bestimmt. Die zu den Monoximen 1 und 2 gehörigen Anionen sind mesomeriestabilisiert. Bei den quaternären Ammoniumkationen 1a, 1b, 1d und 2g wird daher in erster Stufe die Oxim-, in zweiter Stufe die Ammoniumgruppierung deprotoniert. Für die lg cK11 bzw. lg cK12 der Verbindungen 1 und 2 besteht eine lineare Freie-Energie-Polare-Energie-Beziehung. Von den verschiedenen Protonierungsstufen der Dioxime 3 existieren Tautomere. Die von den Amindioximen 3 d, 3e und 3 f abgeleiteten quaternären Ammoniumkationen können daher in erster Stufe sowohl ein Ammonium- als auch ein Oximproton abspalten, und sie unterscheiden sich damit charakteristisch von 1 a, 1 b, 1 d und 2 g.
    Additional Material: 1 Ill.
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus 2-Desoxyribose bildet sich in saurem Medium 3-Acetylacrolein. Dieses reagiert mit 3,5-Dihydroxytoluol (Orcin) im Sinne einer aldolartigen Aldehyd-Phenol-Kondensation über eine zwischengeschaltete Oxydation zu einer Reihe violetter und blauer Farbstoffe. Die Hauptkomponenten wurden präparativ dünnschichtchromatographisch dargestellt und als 9-(2-Acetylvinyl)-dimethyl-hydroxy-3-isoxanthone 2 und 1-(Dimethyl-3-isoxanthonyl)-2-[(dimethyl-dihydroxy-9-methyl-xanthenyl)-9]-äthylene 4 charakterisiert. Die Bildung von 4 erfolgt aus 2 und Orcin. Die Farbstoffe haben den Charakter von Säure-Base-Indikatoren mit stark pH-abhängigen Elektronenspektren. Sie sind in protonisierter Form die Träger der Farbreaktion (2: λmax = 575 nm; 4: λmax = 595 nm).
    Additional Material: 8 Ill.
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 371-376 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The condensation of acetylacetone with anthranilic acid in presence of piperidine as the condensing agent gives acetylacetoneanthranilic acid SCHIFF'S base (H2AA) which forms complexes with Zinc (II) and Palladium (II). The dissociation constants of H2AA have been determined by interpolation at half n̄ values and also by algebraic method which give the values 4.85 and 8.25 at 30° ± 1 °C for the dissociation constants. The stability constants of Zinc (II) and Palladium (II) complexes have been determined adopting CALVIN and MELCHIOR'S extension of BJERRUM'S method and the values of log k1 are found to be 2.92 and 3.97 respectively at 30° ± 1 °C. In these complexes 1:1 metal-ligand stoichiometry is observed.
    Additional Material: 4 Ill.
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  • 133
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 411-421 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: It seems advisable to investigate polycondensation processes extended systematically from low to high conversion by carefully chosen model systems, considering the statistical data available on the processes themselves and the relationship between structure and properties of the resulting polymers. In a previous paper (Rev. Gén. Caoutchouc Plastiques, Éd. Plastiques, 4, (1967) 111) dealing with conventional crosslinking agents, the possibility was suggested to perform polycondensation processes approaching more closely the classical random distribution. This can be achieved with symmetrical monomers having functional groups well spaced out to avoid substitution effects and cyclisation. Cyclisation is also rendered more difficult by greater stiffness of the structure of the monomers. This paper shows by some examples that, in favourable cases, the deviation from the classical random distribution can be reduced to the limits of experimental error, thus enabling the physical properties to be compared with the results of comparatively simple model calculations.
    Notes: Es ist ratsam, Polykondensationsprozesse an äußerst sorgfältig gewählten Modellsystemen zu studieren, und zwar systematisch von niedrigeren nach höheren Umsätzen, und indem man die Kenntnis der Prozesse selbst, der resultierenden Struktur der Produkte, und deren strukturgebundenen physikalischen Eigenschaften gleichzeitig auf statistischer Basis vertieft. In einem früheren Bericht (Rev. Gén. Caoutchouc Plastiques, Éd. Plastiques, 4, 1967, 111) über bekannte organische und anorganische Netzformer wurde auf die Möglichkeit hingewiesen, Polykondensationssysteme zu entwickeln, die den reinen klassischen Zufallsverteilungen in viel besserer Näherung folgen. Hierzu wählt man symmetrische Monomere mit räumlich weit auseinanderliegenden Funktionen, um Substitutionseffekte und Ringschlüsse weitgehend zu vermeiden; weiterhin werden Ringschlüsse auch durch Steifheit der Monomerstruktur sehr erschwert. In diesem Vortrag wird an einigen Beispielen belegt, daß man so tatsächlich die Abweichungen vom klassischen (cyclenfreien) Zufallsmodell in günstigen Fällen erwartungsgemäß bis zur Grenze der Unmeßbarkeit zurückdrängen kann, und daß sich das deshalb lohnt, weil man dann physikalische Eigenschaften der Produkte mit relativ einfachen Modellrechnungen vergleichen kann.
    Additional Material: 7 Ill.
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  • 134
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 422-446 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: The non-equilibrium polycondensation is one of the processes developed in the efforts taken to discover new routes of syntheses in polymer chemistry. It applies to various routes of synthesis, such as polyrecombination, oxidative dehydropolycondensation, polycyclisation, polycondensation of dicarboxylic acids with diamines or bis-phenols and others.The characteristic features of the non-equilibrium polycondensation consist in the absence of reversible equilibrium reactions, high values of the equilibrium constants leading practically to the irreversibility of the process and, in contrast to equilibrium polycondensation, the possibility to prepare copolymers exclusively from monomers. In addition, it offers the essential advantages residing in the wider molecular weight distribution than that of polymers obtained by equilibrium polycondensation.The paper describes experimental results demonstrating the advantages of the non-equilibrium polycondensation. Various examples are presented that prove the non-equilibrium polycondensation a promising process for the synthesis of commercially valuable polymers.
    Notes: Die Entwicklung synthetischer Richtungen in der Polymerchemie führte zu einer Reihe neuer Syntheseverfahren, darunter auch der Nichtgleichgewichts-Polykondensation. Diese umfaßt die Polyrekombination, die oxydative Dehydropolykondensation, die Polycyclisierung, die Polykondensation von Dicarbonsäurechloriden mit Diaminen oder Bisphenolen u. a.Die Merkmale der Nichtgleichgewichts-Polykondensation sind: Fehlen reversibler Reaktionen während der Synthese; hohe Werte der Gleichgewichtskonstante und damit eine Nichtumkehrbarkeit des Prozesses sowie die Möglichkeit, im Gegensatz zur Gleichgewichts-Polykondensation Copolymere nur aus Monomeren zu erhalten.Ein wesentlicher Unterschied besteht auch in einer breiteren Verteilung der relativen Molekülmassen als bei Produkten, die durch Gleichgewichts-Polykondensation erhalten werden.Im Vortrag werden experimentelle Befunde mitgeteilt, die die genannten Besonderheiten der Nichtgleichgewichts-Polykondensation anschaulich illustrieren. An einer Reihe von Beispielen wird gezeigt, daß die Nichtgleichgewichts-Polykondensation ein aussichtsreiches Verfahren von praktisch wertvollen Polymeren ist.
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  • 135
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 294-300 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,5-Diacyl-2-alkyl-diaminoguanidine 1 cyclisieren unter Wasserabspaltung zu 3-(Nα-Alkyl-Nβ-acylhydrazino)-5-aryl-1,2,4-triazolen 3. Die Cyclisierung der 1-Acyl-2-alkyl-5-carbamoyldiaminoguanidine 2 führt zu 2-Alkyl-3-[semicarbazido-(1)]-5-aryl-1,2,4-triazolen 5. Aus 3 und 5 lassen sich durch Säurehydrolyse die entsprechenden Hydrazinotriazole 4 und 6 darstellen.
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  • 136
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 301-308 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wurden hochtemperaturbeständige Azopigmente auf der Basis von 3-Amino-phthalsäureimid hergestellt. Durch Einführung von Chlorsubstituenten konnte die Lichtechtheit günstig beeinflußt werden. Die Migrationsechtheit wurde durch Molekülverdopplung entscheidend verbessert.
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  • 137
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 385-386 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 138
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 447-460 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: The concept of tacticity, originally established for vinyl polymers, is shown to be valid also for condensation polymers if extended to include some particularities. From this point of view the preparation and properties of exclusively isotactic polyesters from lactic acid and substituted β-hydroxy propionic acid are described. Ditactic polyurethanes were prepared from tartaric acid esters. In contrast to tactic vinyl polymers, the condensation polymers obtained show optical activity.A special kind of steric regularity was found to be possible in polyesters and polyamides having built-in single bonds with hindered rotation. Thermal isomerisation of these polyesters may result in removal of their tacticity. The kinetics of this reaction were investigated.Cis-tacticity and trans-tacticity was observed to occur in condensation polymers having C=C or N=N double bonds in the backbone chain. The preparation of some of these polymers is reported, including experiments based on a photolytic polyreaction. The application of catalysts or light led to isomerisation at the double bonds.
    Notes: Der Begriff der Taktizität wurde ursprünglich nur für Vinylpolymere konzipiert; es wird gezeigt, daß er unter Berücksichtigung einiger Besonderheiten auch auf Polykondensate anwendbar ist. Unter diesem Gesichtspunkt werden Herstellung und Eigenschaften von rein isotaktischen Polyestern auf der Basis von Milchsäure und substituierten β-Hydroxypropionsäuren geschildert. Beispiele für ditaktische Polyurethane lassen sich von Weinsäure-Estern ableiten. Zum Unterschied von taktischen Vinylpolymeren sind diese genannten Polykondensate optisch aktiv.Eine besondere Art von sterischer Regelmäßigkeit ist bei Polyestern und Polyamiden durch den Einbau von drehungsbehinderten Einfachbindungen möglich. Bei diesen Polyestern kann die thermische Isomerisierung zum Verlust der Taktizität führen. Die Kinetik dieser Reaktion wird studiert.Cis-Taktizität oder trans-Taktizität kann bei Polykondensaten mit C=C- oder N=N- Doppelbindungen in der Hauptkette auftreten. Die Herstellung von einigen derartigen Polymeren wird beschrieben; unter anderem wird eine photolytische Polyreaktion erprobt. Durch Einwirkung von Katalysatoren oder Licht tritt Isomerisierung an den Doppelbindungen ein.
    Additional Material: 2 Ill.
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  • 139
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971) 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 140
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 561-568 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Herstellung von Estern aus Alkalisalzen verschiedener Carbonsäuren mit Alkylhalogeniden in Gegenwart von tertiären Aminen oder quartären Ammoniumsalzen wird am Modellbeispiel Natriumbenzoat/Benzylchlorid/Triäthylamin untersucht und die Abhängigkeit der Reaktion von verschiedenen Parametern bestimmt. Die Ergebnisse sind durch die Annahme einer zusätzlichen Reaktionsphase an der Festkörperoberfläche erklärbar. Als Katalysator wirkt das quartäre Ammoniumion, tertiäre Amine sind nur als Vorstufe anzusehen.
    Additional Material: 9 Ill.
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  • 141
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 594-601 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Arylidene-2-phenyl-2-imidazolin-5-ones 1 react with Grignard reagents in a boiling ether-benzene mixture to yield 4-diarylmethyl derivatives 2 together with their oxidation products 3 and 4. The exocyclic double bond in 5 also undergoes addition reaction with the same reagents to yield 4-triarylmethyl derivatives 6. Alkylation of 2 affords the 4-alkylimidazolones 7 and 8.
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  • 142
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 579-584 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acidity constants of 3-, 4- and 5-chloro-o-toluidinium ions have been measured at 25° in aqueous dioxane media containing 20, 45, 70 and 72 wt.% of 1.4-dioxane by pH metry. The necessary correction factors to convert pH meter readings into stoichiometric pH have been evaluated. The relation between the strength of anilinium ions and various solvent properties has been discussed. A HAMMETT type relation has been developed for correlating the acid strength of these disubstituted anilinium ions with HAMMETT's structural parameters.
    Additional Material: 3 Ill.
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  • 143
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 642-645 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phenylazocarbonamide liefern nach N-Chlorierung mit tert.-Butylhypochlorit in Chloroform in einer Fragmentierungsreaktion kristallines Phenyldiazoniumchlorid 4 in hoher Ausbeute. Auch N-Chlor-cyclohexyl-azocarbonamid ist fragmentierbar.
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  • 144
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 686-698 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Umsetzung von o-Xylylendihalogeniden mit Ammoniak und einigen seiner Derivate (Benzylamin, N,N-Diphenylhydrazin, Carbonsäurehydrazide, Harnstoff, Cyanamid) liefert Isoindolin 2, 2-substituierte Isoindolin- und o-Xylylendiaminderivate.Eine neue Methode zur Darstellung von 2 aus o-Xylylendihalogeniden und Cyanamid wird beschrieben.
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  • 145
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 706-714 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of 4-arylazo-2-alkoxy-2-thiazolin-5-ones 4a-f with glycine or phenylhydrazine effects their conversion into 1-aryl-5-alkoxy-1 H-1,2,4-triazole-3-carboxylic acid derivatives 5a-j, with the loss of hydrogen sulfide. On the other hand, the reaction of the 2-ethoxy (4a-c) and the 2-isopropyloxy (4g-i) derivatives with strong basic amines involves the loss of an alkyl mercaptan to yield the N-substituted amines 7d-j of 1-aryl-Δ2-1,2,4-triazolin-5-one-3-carboxylic acids. The 2-benzyloxy derivatives 4d-f react with the same reagents to give the N-substituted amides 2a-g of 1-aryl-Δ2-1,2,4-triazolin-5-thione-3-carboxylic acids, with the loss of benzyl alcohol.Hetero-ring opening of 4, followed by recyclisation, occurs upon treatment with ethyl or phenyl magnesium halides to yield the triazolinethione derivatives 13 a-c.
    Additional Material: 2 Tab.
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  • 146
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 722-729 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird über Versuche zur Synthese von 1,3-Oxathiolium-Salzen aus S-Ketomethylen sowie o-Hydroxyphenyl-thiolester-Derivaten berichtet. Die Salze bilden sich nur bei der Einwirkung von starken Mineralsäuren (HClO4) auf o-Hydroxyphenyl-thiolester bzw. auf ihre zugehörigen Ausgangsverbindungen, während unter gleichen Bedingungen die entsprechenden S-Ketomethylenderivate nicht reagieren. Diese cyclisieren dafür aber in Gegenwart überschüssiger Thiosäuren zu 1,3-Dithiolium-Salzen, deren Struktur, ebenso wie die der 1,3-Oxathiolium-Salze, an Hand analytischer und spektroskopischer Daten gesichert wurde.
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  • 147
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 754-762 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: IR-Spektren von höheren und verzweigten Trialkylcyanosilanen bestätigen, daß diese wie das Trimethyl- und Triäthylcyanosilan aus Gemischen der Normal- und Isoform bestehen. Die Alkylgruppen haben auf die Lage der CN- und NC-Schwingungsbanden und auf das Verhältnis von Normal-: Isoform keinen Einfluß. In Bis-[dialkyl(iso)cyano]-disiloxanen, die durch Jodieren der betreffenden Dihydrogendisiloxane und anschließende Umsetzung mit Silbercyanid hergestellt wurden, tritt die Isoform stärker hervor.
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  • 148
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 768-772 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 149
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    Keywords: Chemistry ; Organic Chemistry
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  • 150
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 778-780 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 151
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 889-898 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Infrarotspektren von Butan-, Hexan,- Heptan-, Octan- und Decanarsonsäure sowie von Phenyl-, o-Methylphenyl-, p-Methylphenyl-, p-Äthylphenyl- und p-Diphenyl-arsonsäure werden im Bereich von 400-3500 cm-1 mitgeteilt und die Frequenzen zugeordnet. In den Spektren der Alkanarsonsäuren können im üblichen Erwartungsbereich keine As—C-Valenzschwingungen nachgewiesen werden. Die Bindung eines Phenylringes an den Arsonsäurerest macht die Spektren im Gebiet der AsO-Valenzfrequenzen unübersichtlich. Die Unterscheidung dieser Banden von den CH-out-of-plane-Schwingungen ist unsicher.
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  • 152
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 905-916 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Der elektronenstoßinduzierte Abbau von Trimethylphenoxysilanen (H3C)3Si—O—C6H4R (R = —H und —Cl, —Br, —CH3, —NH2, —NO2 jeweils in ortho-, meta-und para-Stellung) wird beschrieben. Die Hauptfragmentierunsreaktion besteht in der Abspaltung eines Methylradikals vom Molekülion. Für die Ausbeute dieser Reaktion ergibt sich eine HAMMETT-Korrelation. Der Ausdruck lg [(I(M-15)/IM)R(I(M-15)/IM)H] nimmt mit steigendem Wert für die σ-Konstante zu. Diese Abhängigkeit wird auf der Grundlage der Quasi-Gleichgewichts-Theorie der Massenspektren als Folge des Substituenteneinflusses auf die Geschwindigkeit der Spaltungsreaktion und den Anteil der Molekülionen, der die zum Ablauf der Reaktion erforderliche Aktivierungsenergie besitzt, interpretiert. Zur Diskussion dieses Substituenteneffektes werden die mit der Elektronenstoßmethode bestimmten Ionisationspotentiale und die Aktivierungsenergien für die Spaltungsreaktion M+ → (M-15)+ + ·CH3 herangezogen.
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  • 153
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 935-939 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei Reaktion des L-α-Narcotins mit Bromcyan und nachfolgender Hydrolyse entsteht D-β-Narcotin, d.h. es tritt spezifische Inversion nur an C-1 ein. ROBINSON und Mitarbeiter hatten eine spezifische Inversion an C-9 mittels methanolischer Kalilauge verwirklicht. Durch Kombination beider Methoden lassen sich die vier Narcotin-Isomeren sowie die zwei Racemate herstellen.
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  • 154
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 969-976 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3 (5)-Amino-pyrazol liefert mit 1,3-Dicarbonylverbindungen R1COCH2COR2 5, 7-disubstituierte Pyrazolo[1,5-a]pyrimidine. Wenn R1 ≠ R2, erhält man definierte Bicyclen über substituierte 5-Vinylamino-1-p-toluolsulfonyl-pyrazole, z.B. 15, die aus 5-Amino-1-p-toluolsulfonyl-pyrazol, R1COCH2COR2 und katalytischen Mengen Aminsalzen gewonnen werden. Bei der Methylierung von 7-Hydroxy-5-methyl-pyrazolo [1, 5-a]pyrimidin 11 werden 4, 5-Dimethyl-(20a) und 1, 5-Dimethyl-pyrazolo [1, 5-a]pyrimidin- (7) (21a) isoliert. Ein O-Alkyl-Derivat von 11 wird aus 7-Chlor-5-methyl-pyrazolo [1,5-a]pyrimidin und C3H7ONa gewonnen. Die Strukturen 15, 20a und 21a werden durch Diskussion von τ- und J-Werten (1H-NMR-Spektren) für die Pyrazol-Protonen festgelegt.
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 156
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 956-968 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Addition verschiedener elektrophiler Agenzien an ω-Methoxyolefine wurde untersucht, um Aufschluß über eine Methoxygruppenbeteiligung zu erhalten. Eine derartige Beteiligung konnte bei der Addition von Chlor und Brom an 5-Methoxypenten-(1) nachgewiesen werden; hier entstehen zu 10-15% die entsprechenden 2-Halogenmethyltetrahydrofurane, und zu 50-60% tritt Umlagerung unter Verschiebung der Methoxygruppe ein. Die Addition von Chlor oder Brom an 6-Methoxyhexen-(1) liefert zu 15-20% die entsprechenden 2-Halogenmethyltetrahydropyrane, eine Methoxylgruppenwanderung ist nicht nachweisbar. Die Reaktion von Chlor oder Brom mit 4-Methoxybuten-(1) und mit 7-Methoxyhepten-(1) liefert ausschließlich 1, 2-Additionsprodukte.Bei der Anlagerung von Chlor an Allyl-methyl-äther erhält man außer 73% 2,3-Dichlor-1-methoxypropan infolge nebenher ablaufender Dreikomponentenreaktionen 12% 1,2,3-Trichlorpropan, 7% 1,3-Dimethoxy-2-chlorpropan und 8% 1, 2-Dimethoxy-3-chlorpropan. Bei der Addition von 2,4-Dinitrophenylsulfenylchlorid und von Quecksilberacetat an ω-Methoxyolefine tritt weder Umlagerung noch Ringschluß ein. Mit 2, 4-Dinitrophenylsulfenylchlorid entstehen nebeneinander Markownikow- und anti-Markownikow-Produkte, der Anteil des Markownikow-Produktes steigt mit wachsender Kettenlänge vom Allyl-methyl-äther bis zum 7-Methoxyhepten-(1).
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  • 157
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 993-998 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of ternary complexes of the type MAB (where M = Cu(II), Ni(II), Zn(II) or Cd(II); A = nitrilotriacetic acid and B = glycine, α-alanine or dl-aspartic acid) has been shown by potentiometric studies. The nature of titration curves indicates that the secondary ligand B is added stepwise to the initially formed metal nitrilotriacetates. The formation constants (log KMAB) and the free energies of formation (ΔF°) of the mixed complexes have been calculated at 25 ± 1 °C and m̈ = 0.10 (KNO3) at different pH values. The formation constants of the resulting 1:1:1 ternary complexes follow the order Cu(II) 〉 Ni(II) 〉 Zn(II) 〉 Cd(II).
    Additional Material: 3 Ill.
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  • 158
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In conformity with the assumption that light fastness depends upon the electron density of the azo centre, it is now shown that condensation of the aldehyde function in p-aryl azo salicylaldehydes with hydroxylamine, semicarbazide, aniline, phenylhydrazine, 2,4-dinitrophenylhydrazine and ethylene diamine causes in most cases an increase in light fastness on nylon 6 as a result of the decreased electron attracting properties of the functions as compared with the aldehyde function. Aftertreatment of dyeings from arylazo salicylaldehydes or arylazo acetophenone with ethylene diamine causes a similar increase. Further confirmation of this observation is obtained in case of monoazo dyestuffs derived from salicylaldehyde and derivatives which contain the sulphonic acid group when applied as acid dyestuffs on Nylon 6. Application of the latter dyes on wool revealed an analogous tendency only in case of dyes derived from 2-naphthylamine-4, 8-disulphonic acid.
    Additional Material: 5 Tab.
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  • 159
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1051-1059 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es werden die Elektronenanlagerungs-Massenspektren einer Reihe von 22,26-Epiminocholestanen verschiedenen Sättigungs- und Substitutionsgrades sowie unterschiedlicher Stereochemie an C-22 und C-25 vergleichend untersucht. Neben dem M-1-Peak wird als typischer Spaltprozeß bei dieser Verbindungsklasse Fragmentierung zwischen C-20 und C-22 beobachtet, die zu einem um 98 bzw. bei Acetylepiminocholestanen 140 Masseneinheiten unterhalb der Molmasse liegenden Peak führt. Eine Ausnahme bilden Δ22-ungesättigte Vertreter, bei denen eine solche Spaltung ausbleibt und die stattdessen einen charakteristischen, durch Ion-Molekül-Reaktion mit Sauerstoff resultierenden M + 14-Peak zeigen. Daneben tritt in allen Fällen Abspaltung von Wasser bzw. Acetyl auf.
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  • 160
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1070-1080 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Am Beispiel einfacher Methylverbindungen CH3X wurden aus Eigenvektoren und Eigenwerten von Allvalenzelektronenrechnungen in CNDO/2-Näherung Größen berechnet, die der 13C—H-, der geminalen H—H-Kopplungskonstante bzw. der 13C-chemischen Verschiebung der Methylgruppen proportional sein sollen. Die theoretischen Größen werden mit den entsprechenden experimentellen Werten verglichen. Güte und Grenzen der Näherungsverfahren werden diskutiert.
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  • 161
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1101-1109 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mit einem Allvalenzelektronen-SCF-Verfahren - der INDO-Methode - wird die Elektronenstruktur des Tri- und Pentamethincyanins untersucht. An ausgewählten Modellen wird für die möglichen geometrischen Anordnungen der Trimethincyanin-Einzelmoleküle in Doppelmolekülen die relative energetische Stabilität abgeschätzt. Die Berechnungen bestätigen die schon früher festgestellte starke Ladungsalternation und einen weitestgehenden Bindungsausgleich entlang der Polymethinkette. Die Elektronendichteverteilung wird duch die Zusammenlagerung von Trimethincyaninmolekülen zu Doppelmolekülen wenig verändert. Das Modell mit einer „mauerwerkartigen“ Anordnung erweist sich als das stabilste.
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  • 162
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1118-1124 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eine auf Acrylnitril und Hydrazin basierende Synthese von 3(5)-Hydroxy-pyrazol 5a durch Sulfinateliminierung aus 1-(p-Toluolsulfonyl)-pyrazolidon-(3) in nicht-wäßrigem Milieu wird beschrieben. Die Methylierung von 5a liefert Gemische von 5-Hydroxy-1-methyl-pyrazol 5b und 1,2-Dimethyl-pyrazolon-(3) 7. 5b wird chemisch eindeutig durch Sulfinateliminierung aus 2-Methyl-1-(p-toluolsulfonyl)-pyrazolidon-(3), 5-Hydroxy-1-cyclohexyl-pyrazol durch Dehydrieren von 2-Cyclohexyl-pyrazolidon-(3) gewonnen. Die Methylierung von 5a mit 2 Mol p-Toluolsulfonsäure-methylester in DMF liefert in guter Ausbeute 7, analog ergibt 3(5)-Hydroxy-5(3)-methyl-pyrazol 1,2,5-Trimethyl-pyrazolon-(3).
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  • 163
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1125-1130 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phenol und Anilin werden durch Rhodanamin 1 in para-Stellung rhodaniert, p-Toluidin in ortho-Stellung. Acetophenon ergibt unter Verbrauch von zwei Mol 1 2-Amino-4-phenyl-5-rhodano-thiazol 6. Von β-Dicarbonylverbindungen abgeleitete Enamine 7 a, b, c werden zu Rhodan-enaminen 8 a, b, c rhodaniert, aus denen leicht Amino-thiazole, das Dithiin 10 und das Thiazolon 11 erhalten werden können.
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  • 164
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 31-44 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Für die Synthese von heterologen Indanon-(2)-Derivaten werden eine Reihe von ortho-Bis-acetonitrilen und die entsprechenden Diessigsäuren und -ester, wie z. B. Pyrrol- und Thiophen-3, 4-bis-acetonitrile sowie-3,4-diessigsäureester dargestellt. Die DIECKMANN-Cyclisierung führt nur bei dem Thiophenderivat 8 in guter Ausbeute zum gewünschten Ketoester 18, dessen tautomere Formen NMR-spektroskopisch charakterisiert wurden. Aus 18 wird ein Thiophen-Analoges zum Indanon-(2) 19 in hoher Ausbeute erhalten. Dagegen ergibt die Pyrrolverbindung 12 bei gleicher Synthesenfolge nur Spuren des Heterologen 22. Das Ausbleiben des Ringschlusses beim Pyrrolabkömmling aus geometrischen Gründen wird als unwahrscheinlich angesehen.
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  • 165
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der gemeinsamen Einwirkung von Phenolen und N-Methylanilin auf Arylcyanate katalysieren die Phenole die N-Methylanilin-Addition zu Isoharnstoffen und N-Methylanilin die Phenol-Addition zu Kohlensäure-diesterimiden. Die Reaktionen verlaufen über sechsgliedrige übergangszustände und sind durch stark negative Aktivierungsentropien (≈ -43 cal/Mol · grd) gekennzeichnet. Substituenteneffekte wirken sich unterschiedlich aus. Bei substituierten Arylcyanaten ist die Elektrophilie der OCN-Gruppe, bei substituierten Phenolen die Stärke der Assoziate maßgebend für die Reaktionsgeschwindigkeit. In den letzteren Fällen lassen sich daher die Additionsgeschwindigkeiten durch lineare Beziehungen der Form lg k = a · Δ\documentclass{article}\pagestyle{empty}\begin{document}$ \widetilde{v} $\end{document}OH - b beschreiben.
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  • 166
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 115-128 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrazolidon-(3) und dessen C-Alkyl-Derivate werden am N-1 acetyliert und benzoyliert, Aus 1-Acyl-pyrazolidonen-(3) erhält man mit Dimethylsulfat in Wasser oder DMF 2-Methyl-1-acyl-pyrazolidone-(3), mit Benzylhalogeniden in Alkoholen oder Methyläthylketon 2-Benzyl-1-acyl-pyrazolidone-(3), dagegen mit Diäthylsulfat in Alkoholen, Methyläthylketon oder DMF das O-Äthyl-Derivat, z. B. 3-Äthoxy-1-benzyol-Δ-pyrazolin. Die N-2-substituierten 1-Acyl-pyrazolidone-(3) werden sauer zu 2-substituierten Pyrazolidonen-(3) hydrolysiert. Alle Strukturen sind durch kritische Diskussion des chemischen Verhaltens, der IR- und 1H-NMR. Spektren gesichert.Durch Cu-katalysierte saure Dehydrogenierung von 2-Methyl-pyrazolidon-(3) und von 2-Methyl-1-acetyl-pyrazolidon-(3) erhält man nahezu quantitativ 5-Hydroxy-1-methylpyrazol, entsprechend aus 2-Benzyl-pyrazolidon-(3) (8e) 5-Hydroxy-1-benzyl-pyrazol. Die Alkalispaltung von 8e liefert 1-(β-Carboxy-äthyl)-2-benzyl-hydrazin.
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  • 167
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Methyl-penten-(2)-al 1 erhält man durch Aldolkondensation von Propionaldehyd bei 150° an Calciumhydroxid in einer Ausbeute von 42%; bei 300° an 33 Gew.-% Kaliumhydroxid auf Bimsstein in einer Ausbeute von 57% d. Th.Die Kondensation von Propionaldehyd mit Formaldehyd bei 300% an Kaliumhydroxid bzw. Calciumhydrogenphosphat-Kontakten (optimale Katalysatorkonzentration: 10 Gew.-%) liefert 2-Methylacrolein 2 in Ausbeuten von 56-61% (berechnet auf eingesetzten Propionaldehyd).Das Temperaturoptimum beider Reaktionen wurde ermittelt.Der Vorteil dieser Verfahren liegt neben den guten Ausbeuten besonders bei den leicht und billig herzustellenden Katalysatoren. Die Zahl der Nebenprodukte ist gering.
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  • 168
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 153-160 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Als Modellreaktionen zur Aufklärung der Kinetik und des Mechanismus der Oxydation tertiärer C—H-Bindungen durch Permanganat in alkalischen Lösungen wurde die Oxydation von Diphenylessigsäure untersucht. Es wurde gezeigt, daß bis zu Laugenkonzentrationen von etwa 1 m ein Mechanismus unter direktem oxydativen Angriff des Permanganats auf die tertiäre C—H-Bindung überwiegt und im geschwindigkeitsbestimmenden Schritt eine H—übertragung erfolgt. Die Geschwindigkeitskonstante beträgt 3,3 · 10-3 1 mol-1 s-1 bei 20°C und der kinetische Deuteriumisotopieeffekt 7,8.Mit steigender Laugenkonzentration wird in zunehmendem Maße ein radikalischer Mechanismus unter Beteiligung von OH-Radikalen wirksam. Dies drückt sich in einer charakteristischen Zunahme der Geschwindigkeitskonstanten mit steigender Laugenkonzentration sowie in einer Abnahme des kinetischen Isotopieeffektes aus.Es wird eine Variante zur kinetischen Analyse der beiden Mechanismen angegeben und die Geschwindigkeitskonstante für die Reaktion der OH-Radikale mit der tertiären C—H-Bindung zu 1,4 · 107 1 mol-1 s-1 bei 20°C bestimmt.
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  • 169
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 229-235 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Alkyl-, 1-Cycloalkyl-, 1-Aralkyl-, 1-Aryl- und 1-Acyl-pyrazolidone-(3) liefern mit Formaldehyd und sekundären Aminen N-2-MANNICH-Derivate, deren Struktur durch kritische Diskussion ihrer 1H-NMR- und IR-Spektren festgelegt wird. Die hydrogenolytische Spaltung von 2-Morpholinomethyl-1-benzyloxycarbonyl-pyrazolidon-(3) 8c ergibt quantitativ 1-Benzyloxycarbonyl-pyrazolidon-(3) 6c.
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  • 170
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 205-210 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Aminomethylierung von α,ω-Dinitroalkanen entstehen symmetrische Bis-MANNICH-Basen, die nach Überführung in ihre Dihydrochloride zu Dinitroalkadienen thermolysiert werden. Zur Struktursicherung dienen NMR-Spektren und die Addition von p-Toluidin.
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  • 171
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 218-228 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Über entsprechende Phosphorsäure-monoamid-dichloride 5 werden Triamide 8 mit zwei Äthyleniminresten und dem Rest eines hydrophoben Amins synthetisiert, wobei als letzteres neben Heptyl-, Dodecyl-, Cyclohexyl- und β-Phenyl-äthylamin ein antimitotisches α-Phenyl-β-(4-alkoxy-phenyl)-äthylamin (1f, 1g) dient. Eine Methode zur Darstellung von (+)- und (-)-[α-Phenyl-β-(4-äthoxyphenyl)-äthyl]-amid-phosphorsäure-dichlorid 5h und 5i wird angegeben.Aus Phosphoryl-N-Lost-dichlorid 6 wird das Dimorpholid 9k und Bis-(β-phenyl-äthyl)-amid 9e, aus Thiophosphoryl-N-Lost-dichlorid 7 eine Reihe von Thiophosphoryl-N-Lost-diamiden 10 b, 10 d-g, 10i gewonnen. Die Stereoisomerie bei der Kombination von Thiophosphoryl-N-Lost mit zwei Resten der antimitotischen Amine 1f, 1g wird diskutiert. Aus der Diskussion der Cl⊖-Abspaltung u.a. folgt, daß Phosphoryl-N-Lost-diamide des Typs 9k desaktivierte N-Lost-Derivate sind, Thiophosphoryl-N-Lost-diamide dagegen nicht.
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  • 172
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 259-264 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclohexyl- und Butyl-dichlorarsine RAsCl2 reagieren mit Natrium im Molverhältnis 1:2 zu den Cyclopolyarsinen (RAs)n. Während die n-Butyl- und Isobutyl-cyclopolyarsine als pentamere Verbindungen vorliegen, konnten im Falle der Cyclohexyl-, tert.-Butyl- und sek.-Butyl-cyclopolyarsine tetramere Strukturen nachgewiesen werden. Die Molekülgröße wurde durch kryoskopische Molmassebestimmungen und in einigen Fällen auch durch Massenspektren und Röntgenstrukturuntersuchungen ermittelt. Am Beispiel des Tetra-tert.-butyl-cyclotetraarsins wird das chemische Verhalten gegenüber Alkalimetallen, Halogenen und Methyljodid näher studiert.
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  • 173
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 277-286 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acide Verbindungen werden durch Dimethylformamid-dimethylacetal entweder methyliert (Phthalimid, p-Toluolsulfonsäure-methylamid, Phenol, Benzoesäure, Dihexylphosphinsäure, Salzsäure) oder in Tetramethylammoniumsalze (Ditosylimid, 2,4,6-Trichlorphenol, Pikrinsäure, Trifluoressigsäure, Diphenylphosphinsäure) bzw. in Tetramethylformamidiniumsalze (p-Toluolsulfonsäure, Perchlorsäure) überführt. Entscheidend für den verschiedenartigen Ablauf der Reaktionen ist die Acidität der Ausgangsverbindung.
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  • 174
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 339-348 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Am Beispiel der p-Phenylendiamine wird gezeigt, daß mit dem einfachsten quantenchemischen Rechenverfahren, der HMO-Methode, eine Reihe photographischer Eigenschaften, wie Entwicklungsgeschwindigkeiten, Kupplungsgeschwindigkeiten u.a., in Abhängigkeit vom Substituenteneinfluß zufriedenstellend vorausgesagt werden können.
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  • 175
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 331-338 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wurden die integralen Intensitäten charakteristischer Absorptionsbanden im Infrarotgebiet sowie die Dipolmomente einiger substituierter Arylchlorkohlensäureester bestimmt. Die Wurzel aus den integralen Intensitäten wurde mit den HAMMET-Konstanten σ in Beziehung gebracht. So konnte gezeigt werden, daß elektronenaffine Gruppen einen besonderen Einfluß auf die Elektronenstruktur der Chlorkohlensäuregruppe ausüben, der sich vor allem an der Aryl-Sauerstoffbindung bemerkbar macht. Der Einfluß auf die Carbonylgruppe und die Acyl-Sauerstoffbindung ist klein, während der auf die C—Cl-Bindung noch geringer ist.
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  • 176
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971) 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 177
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 357-370 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Zerfallsreaktionen der Tetraalkoxysilane Si[—O—(CH2)nCH3]4 (n = 0-4) und Si[—O—(CH2)nCH(CH3)2]4 (n = 0, 1, 2) bei Elektronenstoß in der Ionenquelle des Massenspektrometers werden wiedergegeben. Sie bestehen im Abbau der primär durch Fragmentierung aus dem Molekülionen gebildeten Ionen (Alkyl-O-)3Si+ und (Alkyl-O-)3Si—OCH2+. Diese Abbaureaktionen sind Folgen von Wasserstoffumlagerungen, in deren Verlauf Aldehyd- und Olefinabspaltungen miteinander konkurrieren. Im allgemeinen überwiegt die Olefinabspaltung. Die Besonderheiten dieser Reaktionen bei der Fragmentierung der verschiedenen Tetraalkoxysilane werden diskutiert.
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  • 178
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 377-384 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mit einer thermokinetischen Methode wurde an einer kontinuierlichen Strömungsapparatur die Kinetik der Cumolhydroperoxidzersetzung mit Schwefelsäure in einem äquimolaren Phenol-Aceton-Gemisch zwischen 40 und 60 °C untersucht. Außerdem wurde der Einfluß von Wasser und Acetophenon im gleichen Temperaturbereich kinetisch verfolgt. Weiterhin konnten die Aktivierungsparameter und die Reaktionsenthalpie ermittelt werden.
    Additional Material: 7 Ill.
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  • 179
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 397-410 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: The paper presents the essential rules underlaying the polycondensation of the title components in organic solvents in the presence of tertiary amines on heating or at comparatively low temperatures. With hydrogen chloride resulting as a low molecular reaction product the condensation proceeds under non-equilibrium conditions. Conducting the condensation at higher temperatures, however, may be accompanied by destructive exchange reactions of the polymer with the starting material or between the polymer molecules themselves, affecting the molecular weight of the polymers obtained. Investigations of the kinetics of polycondensation of terephthalic acid with 9,9-bis-(4-hydrophenyl)-fluorene and 4,4′-(hexahydro-4,7-methyleneindan-5-ylidine)-diphenol at 150 to 200°C in a solvent with high boiling point showed the polyesterification to proceed by an anionic mechanism with formation of acylium ions at the start of and during the reaction.The polycondensation of dicarboxylic acid chlorides with bisphenols was found to depend largely on the components and composition of the initial mixture, temperature and other factors involved. Particularly, the kind of medium chosen for the polycondensation process reflects in the supramolekular structure and, thereby, in the physical properties of the polymer obtained.The results of experiments carried out to clarify the importance of tertiary amines in the polyesterification reaction in solvents at low temperature suggest two catalytic mechanisms, a nucleophilic and a general basic one.
    Notes: Im Vortrag werden die wichtigsten Gesetzmäßigkeiten der Polykondensation von Dicarbonsäurechloriden mit Bisphenolen in einem organischen Lösungsmittel unter Erwärmen oder bei relativ niedrigen Temperaturen in Gegenwart eines tertiären Amins betrachtet. Im Hinblick auf das niedermolekulare Reaktionsprodukt-Chlorwasserstoff-ist die Polykondensation dann ein Nichtgleichgewichtsprozeß. Wird sie jedoch bei höherer Temperatur durchgeführt, so können destruktive Austauschreaktionen des entstehenden Polykondensats mit den Ausgangsstoffen und zwischen den Makromolekülen auflaufen, wodurch die Molmassenverteilung der Polyarylate beeinflußt wird.Aus Untersuchungen zur Kinetik der Polykondensation von Terephthalsäurechlorid mit 9,9-Bis-(4-hydroxyphenyl)-fluoren und 5,5-Di-(4-hydroxyphenyl)-perhydro-4, 7-methylenindan in einem hochsiedenden Lösungsmittel bei 150 bis 300 °C geht hervor, daß die Polyveresterung nach einem ionischen Mechanismus unter Bildung von Acylium-Ionen verläuft.Von Bedeutung für die Polykondensation von Dicarbonsäurechloriden mit Bisphenolen sind: Verhältnis und Natur der Ausgangsstoffe; Reaktionstemperatur und Art des Mediums. Die Natur des Mediums beeinflußt die Ausbildung der übermolekularen Struktur des Polykondensats.Für die Polyveresterung durch tertiäre Amine bei niedrigen Temperaturen wird eine nucleophile Katalyse und eine allgemeine Basenkatalyse diskutiert.
    Additional Material: 1 Ill.
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  • 180
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 387-396 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: The theory of Flory is extended to include the polycondensation in solution. The rate of the process is shown to be affected by the reactivity of the functional groups and their accessibility, considered to be the probability of interactions resulting in reactions. The accessibility depends strongly on the degree of coiling of the reactants.Calculations were performed to test the concept of the dependence of the polycondensation in solution on the chain length of the polymer and the nature of the solvent. The activation energy was found to increase with the degree of coiling of the reactants.The model reaction of 2, 2-bis-(p-hydroxyphenyl)propane with phenyl chloroformate and the polycondensation of 2,2-bis-(p-hydroxyphenyl)propane with its bis-chloroformate were investigated in the mixed solvents nitrobenzene/decaline and nitrobenzene/p-dichlorobenzene. With the first solvent the polarity and the dissolving quality decrease with increasing content of decaline. In the second mixture only the polarity changes with the content of dichlorobenzene.The rate of the model reaction is hardly affected by the composition of the solvent mixture.In the polymer system the rate is likewise hardly affected if only the polarity of the solvent mixture is changed. Lower dissolving quality caused differences of the kinetic constants ranging over one order. The results seem to support the theoretical considerations.
    Notes: Es wird eine Erweiterung der FLORYschen Theorie für Polykondensationsreaktionen in Lösung vorgeschlagen. Danach wird die Prozeßgeschwindigkeit vor allem von zwei Faktoren beeinflußt, von der Reaktivität der funktionellen Gruppen und von ihrer Akzessibilität - der Wahrscheinlichkeit einer zur Reaktion führenden Wechselwirkung. Die Akzessibilität ändert sich ihrerseits stark mit dem Knäuelungsgrad der Reaktanten.Zur Prüfung der Konzeption, daß die Kinetik von Lösungspolykondensationsreaktionen von der Kettenlänge der Makromoleküle und von der Natur des Lösungsmittels abhängt, wurden Berechnungen vorgenommen. Sie ergaben, daß die Aktivierungsenergie von Polykondensationsreaktionen in Lösung mit dem Knäuelungsgrad der Reaktanten zunimmt.Experimentell untersucht wurde die Modellreaktion von 2, 2-Bis-(p-hydroxyphenyl)propan und Chlorkohlensäurephenylester sowie die Polykondensation von 2, 2-Bis-(p-hydroxyphenyl)propan mit dessen Bis-chlorkohlensäureester in den Lösungsmittelgemischen Nitrobenzol/Dekalin und Nitrobenzol/p-Dichlorbenzol. Im erstgenannten System sinken Polarität und Lösungsmittelgüte für das Polymere mit steigendem Dekalingehalt. In der zweiten Mischung ändert sich mit dem Dichlorbenzolanteil nur die Polarität.Die Geschwindigkeit der Modellreaktion wird durch die Zusammensetzung des Lösungsmittels kaum beeinflußt.Beim makromolekularen System wird die Reaktionsgeschwindigkeit ebenfalls nur gegeringfügig beeinflußt, wenn man allein die Polarität des Lösungsmittelgemisches verändert. Bei Verringerung der Lösungsmittelgüte dagegen treten Unterschiede in den kinetischen Konstanten von einer Größenordnung auf. Diese Ergebnisse scheinen die Richtigkeit der theoretischen Erörterungen zu bestätigen.
    Additional Material: 3 Ill.
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  • 181
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 461-483 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: Siloxane oligomers containing two hydroxyl, amino or anhydride groups were obtained by applying the reactions known to lead to Si—C bonds.Polycondensation of these monomers with suitable bifunctional reactants resulted in siloxane-modified polyesters, phenolformaldehyde resins, polyamides, polyestermides and polyimides the properties of which, such as softening point, solubility and thermostability were investigated. The siloxane containing polyimides proved to be soluble and melting polymers that resisted heating up to 400 degrees C in the presence of air oxygen.Polyimides of similar properties but being composed of different siliciumorganic units were obtained by polycondensation of an imide-containing bis-silanol with dichloro-Si compounds. This process eliminates the laborious preparations of siliciumorganic diamines.Condensation polymerisation of organic polymers with siliciumorganic polymers having one or two reactive functional groups in their molecules allow to prepare siloxane-modified block and graft polymers as well cross-linked products.
    Notes: Mit Hilfe der bekannten Reaktionen zur Knüpfung von Si—C-Bindungen haben wir oligomere Polysiloxane mit zwei Hydroxyl-, Amino- und Anhydridgruppen hergestellt:Durch Polykondensation dieser Monomeren mit geeigneten bifunktionellen Partnern wurde eine Reihe siloxanmodifizierter Polyester, Phenol-Formaldehydharze, Polyamide, Polyesterimide und Polyimide synthetisiert und einige ihrer Eigenschaften (z. B. Erweichungspunkt, Löslichkeit, Thermostabilität) untersucht. Die siloxanhaltigen Polyimide waren beispielsweise löslich, schmelzbar und in Gegenwart von Luftsauerstoff bis gegen 400 °C beständig.Polyimide mit ähnlichen Eigenschaften, aber verschiedenen siliciumorganischen Bauelementen waren durch Polykondensation eines imidhaltigen Bis-Silanols mit Dichlor-Si-Verbindungen zugänglich. Bei diesem Verfahren erübrigt sich die präparativ oft aufwendige Synthese der entsprechenden siliciumorganischen Diamine.Polykondensationsreaktionen von organischen mit siliciumorganischen Polymermolekülen, die eine oder zwei zur Reaktion miteinander befähigte funktionelle Endgruppen besitzen, ermöglichten den Aufbau von siloxanmodifizierten Block- und Pfropfcopolymeren sowie vernetzten Produkten.
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  • 182
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 529-545 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: Phosphorus-containing polymers are known to have valuable properties, primarily the ability of self-extinction. Most favorable results were obtained with substances including phosphorus and chlocrine in their molecules. However, up to now attention was given predominantly to polymers having C—O—P bonds.The present paper describes the synthesis of phosphorus and phosphorus and chlorine containing polymers with C—P bonds using methylol derivatives of phosphorus. Bis-(p-carbomethoxyphenoxymethyl) methylphosphinoxide was used as a phosphine oxide derivative. This phosphorus-containing dicarboxylic acid was reacted with glycols to give phosphorus-containing polyesters and copolyesters. With glycols in excess the reaction led to phosphorus-containing and mixed oligomers which after reaction with diisocyanates yielded polyurethanes, copolyurethanes and urethane block copolymers.Esterification of bis(hydroxymethyl)phosphonic acid with acrylic and methacrylic acid yielded monomers which, when subjected to polymerisation, gave phosphorus-containing polyesteracrylates and methacrylates and, in addition, could be copolymerised with acrylic and methacrylic acid.Mono- and dicondensation products of hypophosphorous acid with chloral, being considered as chlorine-containing methylol derivatives of phosphinic and phosphonic acids, led to polyurethanes.
    Notes: Bekanntlich neigen phosphorhaltige Polymere zum Selbstverlöschen. Die besten Ergebnisse wurden erzielt, wenn im Molekül gleichzeitig Phosphor und Chlor vorhanden sind. Meist wurde jedoch bis jetzt den phosphorhaltigen Polymeren mit C—O—P-Bindungen Aufmerksamkeit gewidmet.Von uns wurden Polymere mit C—P-Bindungen synthetisiert, die nur Phosphor oder gleichzeitig Phosphor und Chlor enthalten. Zu diesem Zweck wurden einige Methylolderivate des Phosphors herangezogen. Von Derivaten des Phosphintyps wurde Bis-(p-carbomethoxyphenoxymethyl)-methylphosphinoxid als phosphorhaltige Dicarbonsäure herangezogen. Durch Umsetzung dieser Säure mit Glykolen wurden phosphorhaltige Polyester und Copolyester dargestellt. Im Falle eines Überschusses der Glykole wurden auch phosphorhaltige und gemischte Oligomere erhalten, aus denen durch Reaktion mit Diisocyanaten Polyurethane, Copolyurethane und Blockpolyurethane synthetisiert werden konnten.Durch Veresterung von Bis-(hydroxymethyl)-phosphonsäure mit Acryl- und Methacrylsäure wurden polymerisierbare Monomere erhalten und dann in phosphorhaltige Polyesteracrylate und -methacrylate überführt sowie mit Acryl- und Methacrylsäure copolymerisiert.Mono- und Dikondensationsprodukte der hypophosphorigen Säure mit Chloral können als chlorhaltige Methylolderivate von Phosphin- und Phosphonsäuren aufgefaßt werden; sie wurden bei der Synthese von Polyurethanen verwendet.
    Additional Material: 11 Ill.
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  • 183
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 569-578 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polarographic behaviour of thio-acetic acid (RSH) at dropping mercury electrode (d.m.e.) has been investigated in presence of KNO3 in the pH range 2-10.5 at 30.0 ± 0.2°C in 50% alcoholic medium at 0.2 M ionic strength. Well defined anodic waves were obtained at all pH values in the concentration range studied. At pH 〈 2.2 and 〉 10.5 ill defined anodic waves were obtained. The effect of pH, concentration of RSH, temperature, drop time and alcohol on the wave characteristic and the mechanism of the reaction occurring at the surface of the mercury drop have been studied in detail. A small prewave was also observed at pH 9.1 and 10.5, which has been assigned adsorption characteristics. The reversibility of the reaction mechanism was confirmed by a number of methods. The wave is diffusion controlled and reversible involving one electron transfer process: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm RSH} + {\rm Hg}\rightleftharpoons{\rm RSH}g + {\rm H}^ + + {\rm e} $$\end{document}Mathematical and experimental evidence shows that the anodic wave of RSH at. d.m.e. does not correspond to formation of (RSSR) but to a mercury compound RSHg according to the above equation. The diffusion coefficient and temperature coefficient for (30-45°C) of id at pH 4.0 and 9.1 have been found to be 1.698; 1.965 × 10-6 cm2/sec and 1.08%; 1.20% per degree respectively. The dissociation constant pKa was found to be 4.25 by the plot of E1/2 vs. pH. The linearity of id with RSH concentrations provides a rapid and precise method for the determination of RSH down to 0.2 mM.
    Additional Material: 4 Ill.
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  • 184
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 614-625 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Titelverbindungen wurden NMR-, UV- und CD-spektroskopisch untersucht. An Hand der chemischen Verschiebung der Protonen des Zuckerrestes wurde für alle untersuchten N-β-D-Glucopyranoside eine anti-Konformation nachgewiesen. Das Vorzeichen der Cotton-Effekte der Glucopyranoside und Desoxyribofuranoside hängt außer von der Konfiguration wesentlich von der Struktur des Aglykons ab. Veränderungen in unmittelbarer Nähe des glykosidischen Stickstoffatoms (6-Azathymin- und Pyridazon-(3)-Derivate) führen zu einer Umkehr des Vorzeichens der Cotton-Effekte.
    Additional Material: 5 Ill.
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  • 185
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 602-606 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ausgehend von 2,4,6-Trichlor-5-methyl-pyrimidin läßt sich über 2,4,6-Trifluor-5-methyl-pyrimidin und 5-Methyl-2,4-dibenzyloxy-6-fluor-pyrimidin durch nachfolgende Abhydrierung der Benzylgruppen 6-Fluor-thymin in guter Ausbeute gewinnen. Die Verbindung ist im Gegensatz zu 6-Fluor-uracil in wäßriger Lösung stabil und daher als biologisch aktive Substanz einsetzbar. Mit NH3 oder Benzylamin reagiert 6-Fluor-thymin leicht zu 6-Amino- bzw. 6-Benzylamino-thymin.
    Additional Material: 1 Tab.
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  • 186
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 626-635 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Umsetzung von Brenzcatechincarbonat 1 mit Alkoholen, Aminen und Hydrazinen werden Kohlensäureester, Urethane, Harnstoffe, Semicarbazide und Carbohydrazide hergestellt. Durch thermische Zersetzung von N-Alkyl-carbamidsäure-(2-hydroxyphenyl)-estern 6 werden Alkylisocyanate gewonnen.
    Additional Material: 8 Tab.
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  • 187
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 667-677 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In der Umsetzung von N-Acyl- und N-Äthoxycarbonyl-α-aminoketonen 1 mit Nitrosierungsmitteln wurde eine neue Methode zur Darstellung von 3-Acyl-1,2,4-oxadiazolen 3 gefunden. Als instabile Zwischenverbindungen sind die α-Hydroximinoderivate von 1, die C,N-Diacyl-formamidoxime bzw. C-Acyl-N-äthoxycarbonyl-formamidoxime 2, anzunehmen, welche vermutlich aus den primär gebildeten N-Nitrosoderivaten von 1 entstehen.
    Additional Material: 2 Tab.
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  • 188
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3(1)H-Imidazo[4,5-h]chinoline sind interessante ampholytische Chelatbildner, da sie in koordinativ günstiger Position zu einer N-Donatorfunktion - auf Grund der Tautomerie dieser Verbindungen - eine acide NH-Gruppe enthalten. Durch Kondensation von 5, 7-Dinitro-8-amino-chinolin mit Carbonsäuren unter reduzierenden Bedingungen wurden verschiedene C-2-substituierte 3(1)H-Imidazo[4,5-h]chinoline erhalten, die in Abhängigkeit vom Carbonsäurerest C-5-amino- bzw. -hydroxysubstituiert sind. Die Kondensation von 5-Nitro-7,8-diamino-chinolin mit Carbonsäuren ergibt in Gegenwart von Polyphosphorsäure C-2-substituierte 5-Nitro-3(1)H-imidazo[4,5-h]chinoline. Die Konstitution der erhaltenen Verbindungen wird durch massenspektroskopische Untersuchungen bestätigt. An unterschiedlich 15N-markierten Verbindungen konnte der Fragmentierungsmechanismus verschiedener 3(1) H-Imidazo[4,5-h]chinoline aufgeklärt werden. Durch quantenchemische Berechnungen des 3(1)H-Imidazo[4, 5-h]chinolins und verschiedener Substitutionsprodukte konnten Hinweise über die Lage der Tautomeriegleichgewichte, die Säure-Base-Eigenschaften, das UV-Spektrum sowie über das reaktive Verhalten dieser Verbindungen erhalten werden.
    Additional Material: 13 Ill.
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  • 189
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 715-721 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acetylation of 4-hydroxy-1-thiocoumarin 1 b in the presence of phosphorus oxychloride yields the 3-acetyl derivative 2, which condenses with aromatic aldehydes to give the corresponding 3-cinnamoyl derivatives 3 a-e, and yields 3-arylazo-4-hydroxy-1-thiocoumarins 4 a-d upon treatment with aromatic diazonium salts.Whereas treatment of 1 b with primary amines results in the formation of 4-substituted amino derivatives 5 a-c, 3-acetyl-4-hydroxy-1-thiocoumarin 2 reacts with the same reagents to yield the 3-α-alkyliminoethyl derivatives 7 a-c.Treatment of 1 b with phenylhydrazine affords the 4-phenylhydrazine derivative 5 d. On the other hand, 2 reacts with the same reagent to yield a mixture of the phenylhydrazone 9 and the pyrazolo-1-thiocoumarin 10.
    Additional Material: 1 Tab.
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  • 190
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 737-744 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Umsetzung von Chinonen mit N,N-disubstituierten Aryl-thioamiden in Gegenwart saurer Kondensationsmittel wird ein neuer Typ farbiger heterocyclischer Verbindungen mit kondensiertem 1,3-Oxathiolium-System erhalten. Es wird über die optimalen Herstellungsbedingungen sowie über einige charakteristische Spektraldaten dieser Verbindungsklasse berichtet.
    Additional Material: 1 Ill.
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  • 191
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 785-794 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The condensation of phenyl-, p-tolyl-, p-anisyl-, and p-chlorophenyl isopropyl ketones with dimethyl methylsuccinate in the presence of potassium t-butoxide, gave the crystalline (E)-4-aryl-3-methoxycarbonyl-2-methyl-4-isopropyl-but-3-enoic acidsi.e., Ar and COOCH3 in trans-position. The nomenclature of cis/trans isomers used herein follows the IUPAC 1968 Tentative Rules, Section E, Fundamental Stereochemistry, J. org. Chemistry 35, 2849 (1970). See also: J. E. BLACKWOOD, C. L. GLADYS, K. L. LOENING, A. E. PETRARCA and J. E. RUSH, J. Amer. chem. Soc. 90, 510 (1968); Introduction to Subject Index of Chem. Abstr. 66 (1963). 1 as major products. These esters resisted oxidation, and the position of the double bond was indicated by their infrared absorption, as well as that of some derived products. Their configuration followed from their conversion to the 4-acetoxy-2-naphthoates 2. The condensation also gave oily half-ester fractions which proved to contain small amounts of the (Z)-isomers 5 by their conversion (in low yields) to the oxoindenyl acids 6.
    Additional Material: 9 Tab.
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  • 192
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 811-816 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch radikalische Addition von N-Chlorurethan und N,N-Dichlorurethan an Cholesten-(2), Cholesterylacetat und Androstenolonacetat erhält man die entsprechenden vicinalen Chlorurethane, die mit Alkali zu Carbäthoxyaziridinen und Aziridinen umgesetzt werden.
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  • 193
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 849-854 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new method for preparing 2-mercaptoacetamide and N-alkyl-2-mercaptoacetamides has been described. Electronic spectra of sixteen N-alkyl and N-aryl-2-mercaptoacetamides have been compared with corresponding substituted acetamides and discussed. The results reveal the possibility of an intra-molecular hydrogen-bonding between —NH hydrogen and sulphur of —SH group.
    Additional Material: 3 Ill.
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  • 194
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 882-888 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sowohl durch Umsetzung von α-Brommethyl- als auch von α,α-Dibrommethyl-aryl-ketonen mit Hydrazin lassen sich 1-Amino-4-aryl-1,2,3-triazole darstellen, deren reduktive Desaminierung 1-H-4-Aryl-1,2,3-triazole liefert.
    Additional Material: 2 Tab.
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  • 195
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1065-1069 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Darstellung von 3-Alkyl-50-guanidino-1,2,4-oxadiazolen 1a-x aus Cyanguanidinen und aliphatischen Nitriloxiden wird beschrieben. Hydrolyse und Oxydation der erhaltenen Reaktionsprodukte werden untersucht.
    Additional Material: 1 Tab.
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  • 196
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Konfigurationszuordnung für die Sulfinylgruppe von Sulfoxiden S-alkylierter L-Cystein-Derivate kann, da in dieser Reihe ein Standard existiert, durch Vergleich der ORD- und CD-Spektren, aber auch durch Vergleich enzymkinetischer Daten erfolgen. Das Verhalten bei Ionenaustausch und Chromatographie läßt ebenfalls Schlüsse auf die Absolutkonfiguration am asymmetrischen Schwefelatom zu.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 197
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1113-1117 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Umsetzung von β-Chlorvinyl-methin-immoniumsalzen mit N, N-disubstituierten Thioacetamiden in Essigsäureanhydrid entstehen die neuartigen 2-Dialkylamino-thiapyryliumsalze 10. Diese reagieren mit CH-aciden Verbindungen zu substituierten 2-Methylen-2H-thiapyranen 11. Die UV-S-Absorptionen der Verbindungen 10 und 11 werden mitgeteilt.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 198
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1139-1142 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Hydrierung von 3-Hydroxy-14β-Δ1.3.5(10).8-östratetraenon-(17) 1 werden ent-8α, 13α-Östron 2 und 8α, 14β-Östron 3 erhalten. Die Reaktion wurde sowohl mit optisch aktivem als auch mit racemischem Material durchgeführt.
    Type of Medium: Electronic Resource
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  • 199
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1155-1172 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Das Reaktivitätsverhalten von 18 monosubstituierten Styrolen bei der radikalischen Copolymerisation mit Styrol wird im Rahmen der Näherungen von HÜCKEL und PARISER-PARR-POPLE MO-theoretisch untersucht. Die unter Zugrundelegung verschiedener Modelle errechneten Reaktivitätsindizes werden mit experimentellen r-Werten bzw. den daraus mittels des ALFREY-PRICE-Schemas errechneten Q- und e-Werten korreliert; die erhaltenen Korrelationen werden diskutiert.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 200
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 54 (1971), S. 117-135 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of the presence of trimethylsilyl and triphenylsilyl groups in substituents of anthraquinone on the properties of anthraquinone vat, acid, and dispersion dyes was investigated.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
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