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  • 1970-1974  (11,070)
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  • 101
    Electronic Resource
    Electronic Resource
    Springer
    Pflügers Archiv 352 (1974), S. 121-133 
    ISSN: 1432-2013
    Keywords: Urate ; Protein Interaction ; Uptake by Erythrocytes ; Renal Reabsorption ; Man ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Interaction of urate with human and rat plasma was studied by a dialysis technique at different temperatures. At 4° C a certain fraction of urate is bound to proteins. However, this fraction diminishes with increasing temperature and at 37° C only some 7–8% (in man) and 2% (in rat) interact with proteins. The finding that urate is almost completely filtered in the glomerulus is discussed. In body areas exposed to low temperatures protein binding of urate may be of importance. Urate uptake by erythrocytes is characterized by two components: a fast component equilibrating almost immediately at about 7% in man and 17% in rat and a slow component reaching equilibrium after 60 min, at 28% and 36%, respectively. The process is described by a mathematical formula. Lowering of the temperature mainly diminishes uptake by the slow component withQ 10-values ranging between 1.5 and 4.0. In the observed range of concentrations the uptake process does not saturate. The results at lower pH-values suggest that it is unionized uric acid which is transported by the slow component. Application of the data to kidney medulla supports the hypothesis that erythrocytes and, probably, to a lesser extent plasma proteins serve as vehicles for urate reabsorption in the countercurrent system. Such a temporary interaction enables uric acid to escape recirculation and to leave the kidney medulla.
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  • 102
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    Psychopharmacology 39 (1974), S. 237-244 
    ISSN: 1432-2072
    Keywords: Antagonism ; Fixed Interval ; Scopolamine ; Physostigmine ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The purpose of this research was to determine if 2 drugs, scopolamine and physostigmine which have opposite effects on cholinergic transmission also produce opposite effects on fixed-interval (FI) performance. Scopolamine and a wide range of doses of physostigmine were administered singly and concurrently to a number of rats responding on a FI 2 min schedule. Scopolamine produced a disruption in FI curvature which could be antagonized by physostigmine, but physostigmine by itself produced no consistent change.
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  • 103
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    Springer
    Psychopharmacology 40 (1974), S. 91-99 
    ISSN: 1432-2072
    Keywords: Lithium ; Social Behaviour ; Sex ; Novelty ; Photographs ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Effects of lithium chloride on the social behaviour of male and female rats were measured in unfamiliar and familiar test situations using a photographic technique. Lithium-treated females showed an increase in body contact and a decrease in social distances in comparison with saline-treated controls in both test conditions. Males administered lithium showed increased corner occupancies in the novel test setting while in the familiar test they showed decreased body contact and increased average group social distance in comparison with the saline condition. Further tests in an exploration box confirmed that lithium decreased the general environmental responsiveness of male rats. The results are discussed with reference to the anti-aggressive effect of lithium.
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  • 104
    ISSN: 1432-0878
    Keywords: LRF ; Hypothalamic localization ; Rat ; Ependyma ; Glia ; Light and electron microscopic Autoradiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Light and electron microscopic autoradiographic analysis of the medial basal hypothalamus of rat brains incubated for 30 and 60 minutes in tritiated luteinizing releasing factor (3H-LRF) revealed selective uptake in the form of silver grains over specialized ependyma (tanycytes) and perivascular glial cells in the palisade-contact zone of the median eminence. The functional capacity of tanycytes and glia are discussed in light of these data.
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  • 105
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    Springer
    Cell & tissue research 150 (1974), S. 493-496 
    ISSN: 1432-0878
    Keywords: Serotonin ; Neurotransmitter ; Myenteric plexus ; Rat ; Histofluorescence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Several recent studies suggested that serotonergic neuron-like elements are present in the guinea pig ileum. The present paper reports an extensive study of the digestive tract of the rat with the use of a histofluorescence technique. Administration of the serotonin precursor, tryptophan, associated with a monoamine oxidase inhibitor, did not allow histochemical demonstration of rapidly fading, yellow fluorescent, 6-hydroxydopamine-resistant neurons; conversely such neurons were readily detected in the brain. It is concluded that serotonergic neuron-like elements cannot be detected histochemically in the rat myenteric plexus area after chemical sympathectomy.
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  • 106
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    Cell & tissue research 151 (1974), S. 457-469 
    ISSN: 1432-0878
    Keywords: Juxtaglomerular apparatus ; Rat ; Adrenalectomy ; Renin and secretory granules ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Die Reaktion des juxtaglomerulären Apparates auf Adrenalektomie wurde untersucht. Im Stadium der Nebenniereninsuffizienz, sechs Tage nach der Operation, wurde quantitativ morphometrisch eine Abnahme der Volumendichte der Sekretgranula (von 32% auf 16%) festgestellt. Golgi-Apparat und Ergastoplasma proliferieren stark, wobei insbesondere die erweiterten Cisternen des Ergastoplasmas auffallen.
    Notes: Summary The response of the Juxtaglomerular apparatus to bilateral adrenalectomy was studied in rats. After the sixth postoperative day, symptoms of severe adrenal insufficiency had developed. In the Juxtaglomerular cells, the volume density of the secretory granules decreased from 32% to 16%. The Golgi apparatus and rough endoplasmic reticulum underwent considerable proliferation, the latter showing strikingly enlarged cisternae.
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  • 107
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    Cell & tissue research 151 (1974), S. 525-536 
    ISSN: 1432-0878
    Keywords: Adrenal cortex ; Rat ; Sex differences ; Gonadal hormones ; Karyometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Adrenal glands of adult female rats are heavier than the glands of corresponding male rats. Postpubertal orchiectomy increases the adrenal weight, an effect restored by testosterone replacement. Under the same conditions ovariectomy of 8 weeks duration does not change the adrenal weight while estradiol replacement enhances the relative adrenal weight. Karyometric studies have shown that nuclei in the female zona fasciculata cells are larger (app. 18%) than those of the male. Similar but only slight differences (2%) were observed in the zona reticularis. Orchiectomy results in enlargement of cell nuclei within all zones of the adrenal cortex; testosterone replacement has the opposite effect. Ovariectomy of 8 weeks duration slightly enhances the volume of nuclei of the zona glomerulosa cells, has no effect on the nuclei of the zona fasciculata and reduces the volume of nuclei in the zona reticularis. Estradiol replacement reduces the volume of nuclei of the zona glomerulosa cells but increases nuclear volume in the zona fasciculata and in the zona reticularis. Thus testosterone has an inhibitory effect on the adrenal cortex of the rat while the physiologic effect of estradiol on the morphology of this gland, particularly on the zona fasciculata cells is rather dubious. The author wishes to thank Mrs. B. Westerska and Miss K. Siejak for excellent technical assistance.
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  • 108
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    Cell & tissue research 151 (1974), S. 537-547 
    ISSN: 1432-0878
    Keywords: Adrenal cortex ; Rat ; Sex differences ; Gonadal hormone ; Stereologic studies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Adult female rats have heavier adrenals than males. Orchiectomy increases the adrenal weight, an effect reversed by testosterone. Neither ovariectomy nor estradiol replacement has an effect on absolute adrenal weight. The stereologic analysis of the volume fractions of particular adrenocortical zones have shown that the volume fraction of the zona glomerulosa in females is smaller as compared with males. On the contrary, the volume fractions of the fasciculata and reticularis zones are higher in female than in male rats. In both sexes gonadectomy and gonadal hormone replacement has an effect on the volume fractions of particular adrenocortical zones, these changes being more pronounced due to orchiectomy or testosterone replacement. The adrenal cortex of all experimental groups contains a similar quantity of parenchymal cells. The cytoplasm volume of a single adrenocortical cell is higher in all zones of the female adrenals as compared with the male. Orchiectomy increases the volume of the cytoplasm in fasciculata and reticularis cells. This effect was reversed by testosterone. Neither ovariectomy nor estradiol replacement has an effect on the volume of the cytoplasm in the fasciculata and reticularis cells. These studies have shown that sex differences with regards to rat adrenal size and weight depend upon the “physiologic atrophy” of the male adrenal cortex, while neither ovariectomy (8 weeks after operation) nor estradiol replacement has a conspicuous effect on the morphologic changes of this gland.
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  • 109
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    Cell & tissue research 147 (1974), S. 259-269 
    ISSN: 1432-0878
    Keywords: Nerve endings ; Hair ; Rat ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Palisade-shaped nerve endings of the small normal hairs of the rat snout were examined with the electron microscope (fixation by perfusion). The terminals are located inside the ‘glassy membrane’ in the area of the neck of the hair root. The 10–20 radially arranged terminal axons are in direct contact with the basement membrane of the epithelium of the external root sheath. The axons are surrounded on all sides by leaf-shaped processes of the Schwann cells. The surfaces of these cell processes are marked by numerous vesicle-like invaginations (approx. 1000 Å dia.). Transverse sections from several areas of the palisadeshaped nerve endings are compared with longitudinal sections. In the upper area ‘empty’ vesicles (approx. 500–600 Å in diameter) occur, along with electron-dense vesicles (approx. 800–1100 Å in diameter); in the middle area, the axons are distended and contain accumulations of mitochondria.
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  • 110
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    Cell & tissue research 147 (1974), S. 183-190 
    ISSN: 1432-0878
    Keywords: Kidney ; Rat ; Bowman's capsule ; Experimental hypertension
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The parietal layer of Bowman's capsule was examined in the rat in control animals and in animals made hypertensive by treatment with desoxycorticosterone acetatesaline and by clipping of the renal artery. At an early stage of elevation of blood pressure and, occasionally, prior to elevation of blood pressure, the epithelial cells of this layer showed basal cytoplasmic protrusion and reduplication accompanied by an increase in the thickness of the basement membrane. These changes preceded evidence of glomerular or renal arteriolar pathology. They presumably reflect either a response of this layer to increased blood pressure and modified glomerular function, or a direct effect of the factors that also induces blood pressure elevation. In either case, they imply a greater functional significance for the parietal layer than has usually been attributed to it.
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  • 111
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    Cell & tissue research 148 (1974), S. 57-67 
    ISSN: 1432-0878
    Keywords: Prostate ; Rat ; Cyproterone ; Alterations ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The dorsal lobe and the coagulating gland of the rat prostate were studied after administration of the anti-androgenic compound Cyp A for varying periods (7–20 days). There was a general involution of the organs with macroscopic atrophy and reduced amount of secretory material. Ultrastructurally the cells were pale, contained less organelles as compared with the controls, loss of cytoplasm and reduction both of cell height and width. The major changes also included reduction of the Golgi area, the rough endoplasmic reticulum and the number of free ribosomes. Within the dorsal lobe prominent nuclear changes were found, comprising different types of intranuclear inclusions of membranous configurations. The alterations observed in the present study are similar to the changes which were found in castrated animals and are consistent with atrophy. The results are discussed in relation to the available biochemical and autoradiographic data on the different lobes.
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  • 112
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    Cell & tissue research 150 (1974), S. 95-105 
    ISSN: 1432-0878
    Keywords: Mucosal mast cells ; Rat ; Compound 48/80 ; Degranulation, Release ; Light microscopy ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Mast cells in the tongue and lamina propria of the duodenal mucosa, representing two cell types with different morphological, histochemical and functional properties have been studied under the electron microscope. Both cell types were found to contain similar moderately electron dense and homogeneous granules surrounded by a tight membrane constituting the basic ultrastructural characteristics of mast cells. The mucosal mast cells, however, contained fewer granules per cell and the individual granules often exhibited considerable variation in size. In addition the mucosal mast cells, unlike those of the tongue, peritoneum and skin, had a smooth plasma membrane lacking microvilli and possessed irregularly shaped or lobulated nuclei. In the tongue mast cells, administration of Compound 48/80 caused the formation of vacuoles around the granules, expulsion of granules from the cells and disintegration of the granular matrix, but no changes that could be attributed to 48/80 could be found in the mucosal mast cells.
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  • 113
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    Cell & tissue research 154 (1974), S. 443-470 
    ISSN: 1432-0878
    Keywords: Oocytes and T-prospermatogonia ; Rat ; Quantitative analysis ; Autoradiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Bei der Ratte findet die sexuelle Differenzierung der Gonade zwischen dem 14. und 15. Tag post conceptionem (p.c.) statt. Während dieser Zeit teilen sich die Oogonien und deren Parallelpopulation—die M-prospermatogonien (multiplying prospermatogonia) oder I-Gonocyten—sehr häufig. Um den 17. Tag p.c. tritt die letzte Generation der Oogonien bzw. der M-prospermatogonien in die Mitose. Die Mitosen bilden häufig “synchronisierte Gruppen”. Die postmitotischen Kerne ihrer Tochterzellen—der Oocyten und der T 1 prospermatogonien (primary transitional prospermatogonia) oder II-Gonocyten—sind klein. Ihr Chromatin ist in Form gröberer Schollen der Kernmembran angelagert. Auf diese Weise kommt das typische “krustenförmige” Aussehen bzw. die Ähnlichkeit mit den Prophasen der Oogonien und M-prospermatogonien zustande. Die Oocyten durchlaufen zunächst die G1-phase (etwa 10 Std Dauer) und treten dann—am Ende des Präleptotänstadiums—in die S-phase. Dann passieren sie die verschiedenen Stadien der meiotischen Prophase und treten vom 3. Tag post partum (p.p.) ab in das Dictyotänstadium. Die T1-prospermatogonien hingegen befinden sich etwa 10 Tage lang in der G1-phase, ohne wesentliche morphologische Veränderungen aufzuweisen. Vom 4. Tag p.p. an durchlaufen sie die S-Phase. Die S-Phasen-Dauer (D-S) beider Zellarten beträgt 11.5 Std und wurde durch Doppelmarkierung mit 14C- und 3H-Thymidin bestimmt. Als am besten geeignete Termine für die Bestimmung der D-S erwiesen sich bei den Oocyten der 18. Tag p.c. und bei den T1-prospermatogonien der 5. Tag p.p. Zu diesen beiden Zeitpunkten war die Anzahl der in die S-phase ein-und austretenden Oocyten bzw. T1-prospermatogonien gleich, die Zellen in S-phase befanden sich im “steady state”. Das Kernvolumen der Oogonien und M-prospermatogonien ist etwa doppelt so groß wie das der postmitotischen Oocyten und T1-prospermatogonien. Bis zum 5. Tage p.p. nimmt das Kernvolumen der Oocyten und T1-prospermatogonien um etwa das Fünffache zu. Der Degenerationsindex der Oocyten liegt wesentlich höher als der der T1-prospermatogonien; er ist postnatal besonders hoch. Aus den T1-prospermatogonien gehen am 4. und 5. Tage p.p. durch Teilung die T 2-prospermatogonien (secondary transitional prospermatogonia) hervor. Die Kerne dieses Zelltyps sind etwas kleiner also die der T1-prospermatogonien. Die T2-prospermatogonien treten am 6. Tage p.p. in die Mitose; es entstehen die ersten A-spermatogonien.
    Notes: Summary In the rat (Wistar-WU) sexual differentiation of the gonads occurs between days 14 and 15 post conception (p.c.). At this time the oogonia and their parallel population — the M-prospermatogonia (I-gonocytes)—divide rapidly. On about day 17 p.c., the last generation of oogonia and M-prospermatogonia, frequently arranged in synchronized clusters, enters mitosis. The postmitotic nuclei of their daughter cells—oocytes and T 1-prospermatogonia (II-gonocytes)—are small; coarse flakes of chromatin are associated with the nuclear membrane causing the typical “crustlike” appearance and the similarity with the prophases of oogonia and M-prospermatogonia. After the oocytes have passed a G1-phase of approximately 10 hr, they enter the S-phase at the end of the preleptotene stage. Then they pass the different stages of the meiotic prophase until they enter the dictyate stage from 3 day post partum (p.p.) onwards. The T1-prospermatogonia, on the other hand, spend a long G1-phase of about 10 days without any conspicuous morphological change before entering the S-phase from day 4 p.p. onwards. The duration of the S-pbase (D-S) of both cell types—oocytes and T1-prospermatogonia—as determined by the double labeling method with 14C- and 3H-thymidine is found to be 11.5 hr. The most favourable time for determining the D-S was day 18 p.c. for the oocytes and day 5 p.p. for the T1-prospermatogonia. On these two days the balance was reached between the cells entering and leaving the S-phase. The nuclear volumes of the postmitotic oocytes and T1-prospermatogonia are approximately half the size of those of their precursors. Until day 5 p.p. the nuclear volumes of the oocytes and T1-prospermatogonia increase about fivefold. The degeneration index of the oocytes is considerably higher than that of the T1-prospermatogonia; postnatally it is especially high. T 2 prospermatogonia arise by mitosis of the T1-prospermatogonia on day 4 and 5 p.p. The nuclei of this cell type are smaller than those of T1-prospermatogonia. T2-prospermatogonia enter mitosis on day 6 p.p and give rise to A-spermatogonia.
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  • 114
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    Cell & tissue research 155 (1974), S. 231-243 
    ISSN: 1432-0878
    Keywords: Pinealocyte-resembling cells ; Habenular region ; Sympathetic nerve fibres ; Ontogenetic development ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The cells of the pineal gland, the pineal stalk, and the lamina intercalaris contain 5-HT and are innervated by sympathetic nerve fibres. These peripheral nerve fibres continue rostrally from the lamina intercalaris and run into the central nervous tissue of stria medullaris and the habenular nuclei. Pharmacological treatment to increase the cellular 5-HT content revealed that the sympathetic fibres are in close relation to yellow fluorescent cells embedded in the brain tissue. These yellow fluorescent cells develop very late in the ontogenetic development (three weeks or more postnatally) and are preceded by ingrowth of sympathetic fibres into the brain tissue. The results support the hypothesis that the cells found in the habenular region are of pinealocyte rather than neuronal nature, but it is possible that they differ in certain aspects from the cells of the pineal gland proper.
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  • 115
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    Cell & tissue research 148 (1974), S. 203-211 
    ISSN: 1432-0878
    Keywords: Hypothalamus ; Rat ; Supraoptic nucleus ; Ultrastructure ; Somatic spines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Electron microscopic studies of ultrathin serial sections of the perikarya and adjacent neuropil of neurons of the supraoptic nucleus (SON) of the adult male rat revealed varying forms of two types of somatic spines. One type forms synapses with axons passing the cell, the other, without synapses, appears to serve as a buttress or clasp for adjacent neuronal and glial processes. The synapse-bearing spines lack the usual spine apparatus but contain the flocculent substance often seen in spines. The other spines do not exhibit either of these structures. These somatic spines were also seen in Golgi impregnated preparations but the types could not be distinguished. Certain axons synapse either on a somatic spine of the perikarya or penetrate the glial sheath of the neuron and synapse, usually repeatedly, on the soma in an en passant manner.
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  • 116
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    Cell & tissue research 148 (1974), S. 371-379 
    ISSN: 1432-0878
    Keywords: Pineal gland ; Rat ; Electric coupling areas ; Freeze-etching
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The pineal glands of Wistar rats were fixed in glutaraldehyde and prepared by the freeze-etching technique. With regard to the form and internal structure of pineal cells this technique has revealed nothing essentially new. Synaptic ribbons are very rarely found. A regular diagonal arrangement of membrane attached particles between the Schwann cell and the axon of an autonomic nerve terminal was observed. Three types of contact areas between pineal cells are described. In the first two types, which occur more frequently, the diameter of the area varied from 1000 to 2500 Å, with irregularly aggregated membrane associated particles. The third type, larger but less frequently found, has a surface area of 0.4 μm2 and much more regularly distributed membrane associated particles (ø 88 Å). These contact areas can be considered to be electric coupling areas between pineal cells.
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  • 117
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    Cell & tissue research 147 (1974), S. 285-292 
    ISSN: 1432-0878
    Keywords: Median eminence ; Rat ; Serotonin terminals ; 5,6- and 5,7-Dihydroxytryptamine ; Chemical degeneration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Electron microscopical evidence for the existence of an important serotonergic input to the rat median eminence is presented. This evidence is based on the demonstration of degenerating nerve terminals in the external layer of the rat median eminence following the application of 5,6-dihydroxytryptamine or 5,7-dihydroxytryptamine, drugs known to exert more or less selective toxic effects on central serotonin neurons. The finding of a serotonergic innervation of the median eminence in mammals has important implications for 5-hydroxytryptamine as a modulator of synthesis and/or release of hypothalamic, hypophysiotropic hormones.
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  • 118
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    Cell & tissue research 149 (1974), S. 91-104 
    ISSN: 1432-0878
    Keywords: Anococcygeal muscle ; Smooth muscle ; Rat ; Innervation, adrenergic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The rat anococcygeus muscle, which is known from previous functional and histochemical investigations to be a smooth muscle with a dense adrenergic innervation, was studied by electron microscopic methods. The muscle was found to be organized in small bundles of 2 to 8 muscle cells, which were interconnected by desmosome-like junctions and by gap junctions. Small Schwann cell-axon complexes with 1 to 5 axons appeared to represent the functional terminal nerve pathway. Such axon complexes were located at the periphery of the small smooth muscle bundles, they never penetrated into them. A ratio of approximately 6 small axon complexes per 100 muscle cells was found. After glutaraldehyde fixation axon varicosities contained mainly small empty vesicles. After treatment with 5-hydroxydopamine and permanganate fixation mainly small vesicles with a dense core were found. The neuromuscular distances ranged from 550 to 5000 Å, with a mean of about 2600 Å. True close neuromuscular contacts at a distance below 500 Å with a fusing of basal laminae were absent. The present observations provide a morphological base for the findings of previous electrophysiological and pharmacological studies on the anococcygeal muscle.
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  • 119
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    Cell & tissue research 149 (1974), S. 113-120 
    ISSN: 1432-0878
    Keywords: Adrenal cortex ; Rat ; Sex-hormones ; Ultramorphometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Ultramorphometrisch wurde nach dem Verfahren von Rohr et al. (1971) die äußere Zona fasciculata von Sprague-Dawley-Ratten bei 5 Gruppen zu je 4 Tieren verglichen: Männchen, Weibchen im Diöstrus, Weibchen im Östrus, männliche und weibliche Kastraten (Kastration am 4. Lebenstag). Die Nebennierenrindenzellen der äu\eren Fasciculata sind bei Weibchen gegenüber denen normaler Männchen hypertroph: Weibchen im Diöstrus zeigen gegenüber Männchen größere Einzelzellen mit vermehrtem glattem endoplasmatischem Reticulum, erhöhten Einzel- und Gesamtvolumina der Mitochondrien sowie einem höheren Lipoidgehalt bei stärkerer Dispersion der Liposomen. Dieselben funktionsspezifischen Strukturen nehmen bei den Weibchen im Östrus noch weiter zu. Die Kastration der Weibchen am 4. Lebenstag führt zu einer Reduktion der funktionsspezifischen morphometrischen Parameter unter die Werte der Diöstrus-Tiere. Männliche Kastraten gleichen die Werte ihrer funktionsspezifischen Strukturen weitgehend denen der Weibchen im Diöstrus an. Nach Kastration am 4. Lebenstag zeigen weibliche Tiere somit etwas niedrigere morphonietrische Parameter in der äußeren Zona fasciculata als die männlichen Kastraten.
    Notes: Summary With the method of Rohr et al. (1971) the outer zona fasciculata of Sprague-Dawley-rats was compared ultramorphometrically in 5 groups of 4 animals each: males, females during diestrus, females during estrus, male and female castrates (castration on 4th day of life). Adrenal cortical cells of the outer fasciculata in females are hypertrophic in comparison with those of normal males: females during diestrus show in comparison with males larger individual cells with increased SER, increased volume of the individual mitochondrium and total volume of mitochondria as well as an increased lipoid content together with a more pronounced dispersion of liposomes. The same function-specific structures show a further increase in females during estrus. Castration of females on the 4th day of life leads to a reduction of the function-specific morphometric parameters below the values of the diestrus animals. Male castrates show adaption of the values of their function-specific structures towards those of females during diestrus. Following castration on the 4th day of life, female animals thus show somewhat lower morphometric parameters in the outer zona fasciculata than male castrates.
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  • 120
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    Cell & tissue research 149 (1974), S. 235-243 
    ISSN: 1432-0878
    Keywords: Adrenal zona glomerulosa ; Rat ; Normal ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary This paper reports on an electron microscopic study of the adrenal zona glomerulosa in the normal rat, with special emphasis on the structural diversity of mitochondria in its parenchymatous cells. The mitochondria of cristae may be tubulo-vesicular, plate-like and/or straight tubular, any one mitochondrion containing one or more types of cristae. The mitochondrial features of the zona glomerulosa parenchymatous cells are attributed to the biochemical stages of aldosterone synthesis, taking place in different mitochondria of these cells.
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  • 121
    ISSN: 1432-0878
    Keywords: Hypothalamo-neurohypophysial system ; Rat ; Granule distribution ; Electron microscopy, morphometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Die Neurohypophyse und die neurosekretorischen hypothalamischen Kerngebiete von normalen männlichen und weiblichen Ratten, von trächtigen und durstenden Tieren wurden elektronenmikroskopisch und morphometrisch mit der Fragestellung untersucht, ob sich in den Häufigkeitsverteilungen der mittleren Granula-Durchmesser, bezogen auf die Anzahl der Axone, eine zweigipflige Verteilung ergibt. Bei Kontrolltieren zeigen die Perikarya des Nucleus supraopticus zahlreichere und größere Granula als die Zellen des Nucleus paraventricularis, wobei der Unterschied in den Durchmessern der Granula bei den weiblichen Tieren ausgeprägter ist als bei den männlichen. Beide Kontrollgruppen zeigen in der Neurohypophyse ein zweigipfliges Verteilungsmuster der Granula, wobei die beiden Gipfel bei den männlichen Kontrollen dichter beieinander liegen als bei den weiblichen. Bei den trächtigen Tieren weisen beide Kerngebiete Zeichen gesteigerter Aktivität auf und die Granula in den Zellen des Nucleus paraventricularis sind deutlich größer als bei Kontrolltieren. Zu Beginn der Tragzeit werden relativ große, wahrscheinlich vasopressinhaltige Granula in der Neurohypophyse gespeichert, während sich im letzten Drittel der Tragezeit die beiden Populationen dort nicht mehr unterscheiden lassen. Nach 48 Std. Wasserentzug erscheinen beide hypothalamischen Kerne aktiviert. Auffallend ist, daß die Granula im Nucleus supraopticus deutlich kleiner sind als bei Kontrolltieren. Entsprechend fehlen in der Neurohypophyse große Granula, während Axone mit kleinen Granula vermehrt sind. Nach zehntägiger Durstperiode lassen sich im Nucleus supraopticus, neben sehr typischen morphologischen Veränderungen, morphometrisch ebenfalls deutlich kleinere Granula nachweisen. Im Hypophysenhinterlappen dieser Versuchsgruppe sind die granulahaltigen Axone sehr stark vermindert, und in der Häufigkeitsverteilung fehlen die Granula mit großem Durchmesser während der dem Oxytocin zugeordnete Gipfel unverändert erscheint. In Verbindung mit den elektronenmikroskopischen Befunden lassen sich also aus den Verschiebungen der Verteilungsmuster zwischen den sechs Versuchsgruppen die Granula mit kleinerem Durchmesser oxytocinhaltigen Axonen zuordnen und Granula mit größerem Durchmesser zu den Endigungen, die Vasopressin enthalten. Die morphometrischen Befunde in den neurosekretorischen hypothalamischen Kerngebieten bestätigen diese Zuordnung. Die elektronenmikroskopischen und morphometrischen Befunde werden besonders im Hinblick auf die Hormonverschiebungen zwischen dem “reserve pool” und den “easily releasable pool” diskutiert.
    Notes: Summary A morphometric evaluation of electron micrographs has been carried out from neurosecretory terminals in the neurohypophysis and from the supraoptic and paraventricular nuclei in normal male and female rats as well as in pregnant and water deprived rats. The task of this investigation was to find out whether frequency distribution diagrams of the mean diameter of the neurosecretory granules, plotted versus the number of axons, reveal a grossly bimodal distribution. In normal rats the nerve cells of the nucleus supraopticus (S.O.N.) show more numerous and larger granules than the cells of the nucleus paraventricularis (P.V.N), this difference with respect to the diameter being more pronounced in female than in male animals. In the posterior pituitary lobes the neurosecretory granules exhibit a bimodal distribution, the second peak being situated more closely to the first one in male controls. In pregnant animals both nuclei appear to be activated, and the granules of P.V.N. are distinctly larger as compared to those of female control animals. In early pregnancy larger, i.e. presumably vasopressin-containing granules are stored in the neurohypophysis, while in the last phase before delivery oxytocin-containing neurons and vasopressin-containing ones cannot be differentiated any more. After 48 hrs of thirst both hypothalamic nuclei exhibit signs of increased activation, the diameters of the granules in the S.O.N. being distinctly smaller than in normals. In the neurohypophysis granules with large diameters are lacking, while axons with small granules are more frequent. In the S.O.N. of animals, water deprived for 10 days the diameters of the granules are smaller than normal and in the neurohypophysis the number of granule-containing fibres is strongly reduced. In the frequency distribution diagram granules with larger diameters are lacking whereas the peak, attributed to oxytocin, is not essentially altered. However, from the observed alteration on the distribution patterns of the six experimental groups and in connection with the electron microscopic results the granules with smaller diameters can be attributed to oxytocin-containing axons and the larger ones to vasopressin-containing terminals. Analogous morphometric data have been obtained from the neurosecretory nuclei as well. The electron-microscopic and morphometric observations are discussed with regard to hormone-shifts between the reserve pool and the easily-releasable pool.
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  • 122
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    Cell & tissue research 151 (1974), S. 471-480 
    ISSN: 1432-0878
    Keywords: Juxtaglomerular apparatus ; Rat ; Influence of deoxycorticosterone (DOC) ; Electron microscopy ; Morphometric analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Die quantitativ-morphologische Analyse des juxtaglomerulären Apparates nach DOC-Behandlung zeigte, daß mit der Hemmung der Reninbildung eine Hypoplasie der epitheloiden Zellen des juxtaglomerulären Apparates einhergeht. Der Granulagehalt der juxtaglomerulären Zellen nahm ab; die Kern-Plasma-Relation änderte sich und die Leiomyofibrillen in den Epitheloidzellen nahmen zu. An den übrigen Anteilen des juxtaglomerulären Apparates, insbesondere der Macula densa, wurden keine morphologischen Veränderungen beobachtet. Die DOC-Behandlung führte darüber hinaus zu einer Bildung von Einschlüssen in den Podocyten, den Mesangiumzellen und den Zellen der Bowman-Membran. Die verschiedenen Möglichkeiten, über welche Faktoren die juxtaglomerulären Zellen nach DOC-Behandlung degranuliert werden, werden diskutiert. Das ultrastrukturelle Bild der Epitheloidzellen nach DOC-Behandlung entspricht deutlich einer gehemmten Sekretion, da das Ergastoplasma und der Golgi-Apparat ganz besonders stark zurückgebildet werden.
    Notes: Summary Quantitative morphological analysis of the Juxtaglomerular apparatus of rats treated with deoxycorticosterone (DOC) and salt revealed hypoplasia of the epithelioid cells as a concomitant of the inhibition of renin synthesis. The granular content of the Juxtaglomerular cells was significantly decreased, while the nucleus-to-cytoplasm ratio and the volume density of leiomyofilaments in the epithelioid cells increased. No morphological alterations were observed in the remaining constituents of the Juxtaglomerular apparatus, including the macula densa. DOC-treatment also induced the appearance of inclusions in the podocytes in the cells of the mesangium, and in the cells of Bowman's capsule. The possible mechanisms of degranulation of the Juxtaglomerular cells after treatment with DOC are discussed. The ultrastructural appearance of the epithelioid cells after treatment with DOC corresponds to an inhibition of secretion, since the rough endoplasmic reticulum and the Golgi apparatus undergo marked regressive changes.
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  • 123
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    Langenbeck's archives of surgery 336 (1974), S. 15-23 
    ISSN: 1435-2451
    Keywords: Rat ; Splenectomy ; Gastric Ulceration ; Increase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung An Ratten wurde der Einfluß von Splenektomie auf Magensaftsekretion und Ulcusentstehung untersucht. Sowohl nach “restraint-stress” als auch Pylorusligatur wiesen die splenektomierten Tiere eine ausgeprägte Steigerung der Ulcuszahl und -größe gegenüber den Kontrolltieren auf. In der Magensaftanalyse waren dagegen die Werte der splenektomierten Tiere gegenüber den scheinoperierten nur geringgradig gesteigert. — Als mögliche Ursache der vermehrten Ulcusanfälligkeit nach Splenektomie wurde eine Veränderung lokaler, nicht säuresekretorischer Faktoren der Magenwand diskutiert.
    Notes: Summary In Splenectomiced rats incidence of gastric ulceration was compaired with control groups. Restraint stress and ligation of pylorus was used as model. Splenectomiced rats do show an higher incidence in both models. Both frequency and extension of gastric ulcer were accumulated significantly. Analysis of gastric secretion was only unessentially raised in comparisom to control-groups. Change of protective factors of stomach as possible reason is discussed.
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  • 124
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    Biopolymers 13 (1974), S. 1-27 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe a method for determining chemical kinetic constants and diffusion coefficients by measuring the rates of decay of spontaneous concentration fluctuations. The equilibrium of the system is not disturbed during the measurement. We measure the number of molecules of a specified type in a defined open volume as a function of time and compute the time course of the deviations from the thermodynamic mean concentration. The method is based on the principle that the rates of decay of spontaneous microscopic fluctuations are determined by the same phenomenological rate coefficients as those of macroscopic departures from equilibrium which result from external perturbations. Hence, an analysis of fluctuations yields the same chemical rate constants and diffusion coefficients as are measured by conventional procedures. In practice the number of the specified molecules is measured by a property such as absorbance or fluorescence which is specific and sensitive to chemical change. The sample volume is defined by a light beam which traverses the cell. As the molecules appear in or disappear from the light beam, either due to diffusion or chemical reaction, their concentration fluctuations give rise to corresponding fluctuations of the intensity of absorbed or emitted light. This paper presents the theory needed to derive chemical rate constants and diffusion coefficients from these fluctuations in light intensity. The theory is applied to three examples of general interest: pure diffusion in the absence of chemical reaction; the binding of a small rapidly diffusing ligand to a larger slowly diffusing macromolecule; and a unimolecular isomerization. The method should be especially useful in studying highly cooperative systems, relatively noncooperative systems with intermediate states closely spaced in free energy, small systems, and systems not readily subject to perturbations of state.
    Additional Material: 3 Ill.
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  • 125
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    Biopolymers 13 (1974), S. 97-114 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular conformations and dynamics of poly(L-prolyl), poly(hydroxyl-L-prolyl), poly(L-prolyl-glycyl), poly(hydroxyl-L-prolyl), and poly(glycyl-glycyl-L-prolyl-glycyl), in aqueous solution, have been studied using 13C pulse Fourier transform nmr spectroscopy. From a measurement of the intensities of major and minor resonances in the spectra of the copolypeptides, it was determined that 15-20% of the glycyl-prolyl and glycyl-hydroxyprolyl peptide bonds are cis. Effective rotational correlation times (τeff), obtained from measurements of spin-lattice relaxation times (T1) of individual backbone and side-chain carbons, demonstrated that backbone reorientation is approximately isotropic for the five polypeptides and is characterized by correlation times of ca. 0.3-0.6 nanoseconds as a result of rapid segmental motion. In a given polypeptide glycyl and pyrrolidine residues were found to have the same backbone correlation times, but backbone carbon τeff values did decrease as the glycyl content of the peptides increased. A semi-quantitative analysis of Cβ, Cγ, and Cδ correlation times suggests that rapid ring motion in both prolyl and hydroxyprolyl involves primarily Cγ and Cβ, with the prolyl ring being more mobile than the hydroxyprolyl ring.
    Additional Material: 3 Ill.
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  • 126
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    Biopolymers 13 (1974), S. 237-238 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No. Abstract.
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  • 127
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    Biopolymers 13 (1974), S. 217-226 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A model for the flexibility of DNA is proposed that is based on discrete variations in the direction of propagation in going from one subunit to the next. Expansion of the local free energy in terms of the local bending gives a Gaussian distribution function. The assumption of the independence of local bends on neighbors lead to very simple formulae for the persistence length and the characteristic ratio. Emphasis, however, is placed on the application of the formulae for molecules of finite size where the persistence length and C∞ are not defined. The formulae are worked out for two models, which should serve as limits for the real physical situation.
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  • 128
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    Biopolymers 13 (1974), S. 735-743 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: If dispersion effects are not taken into account, the dimensions of particles in suspension estimated from spectrophotometric data (slope of the log OD versus log λ plot) are too low. By measuring dispersion curves for the medium and for the suspension, a consistent estimate of the size of latex particles of different diameter is obtained from the OD data.
    Additional Material: 3 Ill.
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  • 129
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    Biopolymers 13 (1974), S. 765-768 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The helix-coil transition of poly-N5-(3-hydroxypropyl)-L-glutamine in methanol-water solutions has been observed using 13C nuclear magnetic resonance. Two signals appear in the α-CH region in the course of the transition; this is in contrast with previous proton magnetic resonance experiments carried out on this polymer in the same solvent system.
    Additional Material: 1 Ill.
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  • 130
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    Biopolymers 13 (1974), S. 779-790 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: X-ray diffraction and stereochemical analyses were used to study the hydrated structure of the helical amylose polymorph having a fiber repeat spacing of 8 Å. Intensity calculations using computer models confirmed six as the number of residues per turn and supported the space group P212121. Both diffraction intensity and stereochemical methods indicate the suitability of residue G3 from the potassium acetate complex of cyclohexaamylose as opposed to residues with longer O(4)-O(1) vectors. Comparison of the present results with those obtained for V amylose dehydrate indicated no major conformational differences between the two helix skeletons. A net helical rotation of approximately 30° accompanied the hydrate-dehydrate transition and the rotational position in the hydrate allowed packing that was less close. Hydration water molecules were not located; noncarbohydrate peaks on the electron density maps were primarily due to Fourier series termination errors.
    Additional Material: 4 Ill.
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  • 131
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    Biopolymers 13 (1974), S. 843-852 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have measured the circular dichroism spectra and have obtained melting curves for samples of purified satellite DNA's from three species of crab, Cancer borealis, Gecarcinus lateralis, and Callinectes sapidus. Although all three satellite DNA's have the same density in neutral CsCl, their circular dichroism spectra and melting and reassociation characteristics are different, as are other properties of these DNA's. The circular dichroism spectra are analyzed to give estimates of nearest-neighbor frequencies. We estimate that about 90% of the Cancer borealis satellite DNA and over 80% of the Gecarcinus lateralis satellite DNA consist of d(AT)n:d(AT)n sequences, while the serially repeating unit of the Callinectes sapidus satellite DNA may not contain any extended d(AT)n:d(AT)n sequences. The results from the circular dichroism spectra for the Cancer borealis, Gecarcinus lateralis, and the Callinectes sapidus satellite DNA's are in agreement with base composition analyses, which give 2.4, 8, and 25% G+C, respectively, for these DNA's.
    Additional Material: 3 Ill.
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  • 132
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    Biopolymers 13 (1974), S. 879-890 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Samples of epichlorohydrin crosslinked potato starch were prepared by using a high ratio of starch to water and alkali concentration below the gelatinization level. This yielded crosslinked samples that were partially crystalline, and where the number of crosslinks could be varied between 1 and 20 crosslinks per 100 anhydroglucose units. The degree of swelling varied regularly with degree of crosslinking, and the molecular weight between crosslinks Mc as derived from swelling data in a good swelling agent compared favorably with Mc derived from chemical analysis.From the heat of gelatinization of the crosslinked starches, as observed in a differential scanning calorimeter, for gelatinization in glycerol, water, and dimethylsulfoxide, a model for the gel state of the crosslinked starch is proposed. It is concluded that the entropy of melting is the determining factor in establishing the temperature of gelatinization.
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  • 133
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    Biopolymers 13 (1974), S. 909-917 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichroism studies of the interaction of β-cyclodextrin with a series of eight dinucleoside phosphates, and with 3′-AMP are reported. From results with ApU and ApA, it is shown that β-cyclodextrin binding is sensitive to dinucleoside stacking in approximately the same way as optical measures of stacking. Some qualitative uses of β-cyclodextrin binding are suggested, based on the fact that the change in the CD spectrum caused by cyclodextrin binding is unique to each of the dinucleosides studied. Hoffman and Bock have previously suggested the use of β-cyclodextrin as a probe of nucleic acid structure. Their work indicated that only binding to adenosine and inosine would have to be considered. The present paper shows that binding to other bases cannot be neglected, and will impose serious restrictions on the use of β-cyclodextrin as a structural probe.
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  • 134
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    Biopolymers 13 (1974), S. 987-993 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(1,N6-etheno-2-aza-adenylic acid) [poly(2-aza-εA)] was synthesized from 1,N6-etheno-2-aza-adenosine 5′-diphosphate (2-aza-εADP) and Escherichia coli polynucleotide phosphorylase. The values Km = 1.02 mM, V = 1.06 μmol hr-1 enzyme unit-1 were found for the polymerization reaction. In contrast to polyadenylic acid, this novel fluorescent polymer has a random structure in solution. The application of the 2-aza-εADP for localization of polynucleotide phosphorylase was also described.
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  • 135
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    Biopolymers 13 (1974), S. 1011-1022 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of L-methionine oligomers [BOC-(Met)n-OMe] (n = 2-7) and the corresponding diastereomeric di- and tripeptides were synthesized using the mixed anhydride method. Oligomers prepared in this manner were optically pure and were obtained in reasonable yield. Preliminary optical examination of the peptides suggests that secondary structures may begin forming in the pentamer or hexamer in trifluoroethanol. BOC-(Met)4-OMe and BOC-(Met)5-OMe were also synthesized using an insoluble resin containing BOC-L-methionine as the nitrophenol active ester.
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  • 136
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational studies of a series of oligopeptides (from the tripeptide to the octadecapeptide) with the repeating sequence L-norvalyl-glycyl-L-proline and a polytripeptide with this sequence are reported. By means of chiroptical techniques, unordered conformations are found for all oligopeptides in water, trifluoroethanol, and ethylene glycol and for the water-insoluble polymer in trifluoroethanol. In ethylene glycol the polymer assumes a collagen-like structure. Infrared studies indicate that all the oligomers, in contrast to the polymer, are unordered in the solid state.
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  • 137
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    Biopolymers 13 (1974), S. 1109-1116 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Uncharged poly(Nε-methyl-L-lysine) (PMLL) and its isomer, poly(Nδ-ethyl-L-ornithine) (PELO), in alkaline solution (pH ca. 12) undergo a helix-to-β transition upon mild heating at 50°C or higher in a manner similar to that of poly(L-lysine) (PLL). The rate of conversion follows the order: PMLL 〈 PELO 〈 PLL. The helix can be regenerated upon cooling near zero degrees, for instance, after more than 12 hr at 2°C. At concentrations less than 0.02% the β form is intramolecular, but at higher concentrations both intra- and intermolecular β forms are generated. Poly(Nδ-methyl-L-ornithine) (PMLO), an isomer of PLL, behaves like poly(L-ornithine); uncharged PMLO in alkaline solution is partially helical and becomes disordered at elevated temperatures.
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    Biopolymers 13 (1974), S. 1161-1171 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to study the effect of side-chain length on the conformation of polypeptides, conformational changes of various ionic polypeptides with various lengths of side chain, poly-Nε-glutaryl-L-lysine (PGL), poly-Nδ-glutaryl-L-ornithine (PGO), poly-Nε-succinyl-L-lysine (PSL), and poly-Nδ-succinyl-L-ornithine (PGO), were investigated by ORD, potentiometric titration, and dilatometric measurements in aqueous solution. The results of optical rotation and potentiometric titration measurements indicate strongly that the α-helix stability increases in the sequence PSO 〈 PSL ∼ PGO 〈 PGL, which corresponds to increased side-chain length. The volume change associated with the helix-coil transition also increased in the above sequence. This series of polymers seems to be more hydrophobic compared with poly-L-glutamic acid or poly-L-lysine, as suggested from the values of enthalpy and entropy changes for coil-helix transitions.
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  • 139
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    Biopolymers 13 (1974), S. 1195-1203 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational changes of poly-Nε-glutaryl-L-lysine (PGL) and poly-Nε-succinyl-L-lysine (PSL) in various salt solutions were studied by use of ORD and potentiometric titration measurements. The addition of alkali metal salts to the fully ionized PGL or PSL solution caused helix formation. The helical content of the polymers increases in the following sequences: at salt concentration 0-2 M, CsCl 〈 KCl 〈 LiCl 〈 NaCl; and at 2-3 M, LiCl 〈 CsCl 〈 KCl ∼ NaCl. The preferential binding of the solvent components with various alkali metal salts of PGL or PSL was measured in LiCl, NaCl, and KCl solutions by means of equilibrium dialysis and differential refractometry. It was found that with increasing salt concentration, the polymers were preferentially hydrated in NaCl and KCl soultions; however the salt was preferentially bound to the polymers in LiCl solution. Such preferential binding was suggested to be closely related to conformational change. The addition of CaCl2 to polymer solutions led to the stabilization of the helical structure of PGL or PSL.
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  • 140
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    Biopolymers 13 (1974), S. 1261-1267 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Refractive indices of bovine serum albumin solutions in saline and in 2-chloro ethanol are measured for the spectral region 1770-10000 Å by a reflectance method. A procedure for the determination of a dispersion formula for binary mixtures is developed and applied. The electronic polarizability of bovine serum albumin is determined and is found to be almost independent of the solvent and concentration. Hence it follows that the electronic polarizability of bovine serum albumin is almost independent of the molecular environment.
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  • 141
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    Biopolymers 13 (1974) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 142
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dielectric absorption of poly-DL-phenylalanine and poly-γ-benzyl-L-aspartate (PLAB) was measured in very dilute solutions to determine the type of molecular association and to locate the helix-coil transition. Both polypeptides were present as associated helices in chloroform. The mode of aggregation, which was determined by measuring the dipole moment and the critical frequency, did not depend on the polarity of the side chain but rather on that of the solvent.In both polymers, the dissociation of the aggregates in chloroform was observed on addition of small amounts of dichloroacetic acid; further addition of the acid lead to the helix-coil transition.No second region of dielectric absorption that might be related to the kinetics of the transition was found during the helix-coil transition of PBLA.
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  • 143
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular conformation of some polysaccharides in aqueous solution in evidenced by changes in the optical rotation and in the elution pattern of gel filtration. The changes in the specific rotation against that in water are expressed as a molar conformational value [K]D21: -495° for colominic acid in 1.0 N NaOH solution, and -180° for hyaluronate (HA), +85° for corneal keratin sulfate, and +234° for amylose in 8 M urea solution. The gel filtration of amylose and HA dissolved in 8 M urea solution shows elution patterns distinctly different from those dissolved in water. The phenomena are attributable to a molecular conformational transition of polysaccharide molecules in aqueous solution.
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  • 144
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A previously described procedure for simultaneous optimization of bond lengths and angles was used to test different models for mannan I. Potential hydrogen bonds and the glycosidic angle were included in the optimization. A conformational model with bifurcated intramolecular hydrogen bonds of the type observed in the methyl cellobioside methanol complex showed the best agreement with available exprerimental data. The coordinates of this model were provided by computer calculations. The available X-ray data, however, were not sufficient for selecting this model; rather, ir data were necessary to furnish the needed information. The different conformational models tested all showed an almost constant virtual bond length O(1)-O(4) of the β-pyranose residue. This was in contrast to the previously obtained results for the α-pyranose residues.
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  • 145
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    Biopolymers 13 (1974), S. 1187-1193 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The longitudinal proton magnetic relaxation times T1 were measured for ferri (met)-and carbonmonoxy-bovine haemoglobin and equine myoglobin in 0.1 M KH2PO4 aqueous solutions near pH 6 at 5°C and 35°C from 1.5- to 60-MHz Larmor frequencies. It is concluded that the correlation time τC for the dipole-dipole interaction of electron and nuclear spins is in fact the electron (ferric) spin relaxation time τS being close to 1.5 × 10-10 sec for both metHb and metMb at 5°C. At 35°C the paramagnetic relaxation rates are not determined solely by the relaxation of protons exchanging from the haem pocket with bulk solvent. Hence, τC at 35°C cannot be calculated from the dispersion data obtained at this temperature. The relevance of this for the determination of interspin distances r is discussed.
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  • 146
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    Biopolymers 13 (1974), S. 1213-1222 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The orientation of naphthalene rings in the side chain of poly-γ-1-naphthylmethyl-L-glutamate (PNLG) in mixed solvents of dichoroethane (DCE) and hexafluoroisopropanol (HFIP) has been studied together with its conformation by infrared, circular dichroism, and fluorescence spectra. The CD pattern of PNLG varies with the solvent composition while it maintains the α-helical conformation. The fluorescence spectra of PNLG in solution show excimer emission of the naphthalene chromophores. The ratio of intensity of the excimer emission to that of the normal fluorescence decreases as the HFIP component in the solvent increases. It is suggested that the naphthalene rings in the side chain of α-helical PNLG are more rigidly orientated in the solvents of higher HFIP ratio.
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  • 147
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    Biopolymers 13 (1974), S. 1269-1290 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The near ultraviolet chiroptical properties of L-cystine conformational isomers are examined on a static, “one-electron” model in which the disulfide moiety is the chromophoric group and the atoms of the L-alanyl fragments are treated as perturbers. The zeroth order chromophoric wave functions are calculated on a semiempirical molecular orbital model in which excited states are constructed in the virtual orbital-configuration interaction approximation. The perturbing environment is represented by point charges located at the atomic centers of the L-alanyl fragments. Chromophore-perturber interactions are expressed as charge-multipole moments with only the charge-dipole and charged-quadrupole terms being retained in the calculations. Vicinal contributions to the rotatory strengths of the five lowest energy disulfide transitions are computed for 30 conformational isomers of the L-cystine dizwitterion. The results provide support for the view that vicinal or peripheral effects can account entirely for the observed near ultraviolet (λ 〉 230 nm) chiroptical properties of L-cystine and its derivatives and that these properties are diagnostic of conformational features external to the disulfide moiety.
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  • 148
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroic spectrum of poly(Tyr,TyrBr) in trimethylphosphate from 180 to 320 nm is found to be a linear function of composition from 25 to 68% TyrBr, and the spectra of the Tyr and TyrBr components are resolved. For Tyr the resolved spectrum is in agreement with available CD spectra of poly(Tyr). These results are interpreted to mean that the side-chain conformations of Tyr and TyrBr are not affected by the other component, and that for Tyr the conformation is the same as in poly(Tyr). It is also concluded that poly(Tyr,TyrBr) is helical with the same helix sense as poly(Tyr). The restrictions on the side-chain conformations are discussed, and it is suggested that the Tyr and TyrBr side chains are all in the same χ1 region.
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  • 149
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    Biopolymers 13 (1974), S. 1377-1389 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism of double-helical nucleic acids was calculated as a function of geometry using the theory of Tinoco and Johnson. This theory does not include contributions of near ultraviolet transitions that are not π → π* in nature. The calculated circular dichroism shows a strong dependence on the distance of base pairs from the helix axis and the tilt of the base pair. Smaller dependences are predicted for the propeller-like twist of a base pair and for variation of the angular increment per base pair. Moderately good agreement between calculated and many experimentally observed spectra could be generated.
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  • 150
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    Biopolymers 13 (1974), S. 1427-1434 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The maximum at 220 nm in the circular dichroism spectrum of native collagen solution changed to a negative value after heat denaturation or collagenase hydrolysis. The enzyme induced rate of CD change at 220 nm was shown to be first order in collagen concentration. The specific rate constant k is actually a combined rate constant kfast and kslow in which the ratio kf/ks is 4.1. The initial rates were linear with respect to enzyme concentration, and the Km was found to be 5.5 × 10-7 M. The rate of ultraviolet hyperchromicity at 220 nm on collagen hydrolysis was determined. The kfast was the same as that obtained by CD. The kf/ks ratio was 4.6. Both methods may be readily used to assay for collagenase activity.
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  • 151
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    Biopolymers 13 (1974), S. 1461-1482 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal and molecular structure of the complex of amylose with dimethyl sulfoxide has been studied by a combination of stereochemical analysis, potential energy, and X-ray diffraction methods. The complex crystallizes in a pseudotetragonal unit cell with a = b = 19.17 Å and c (fiber axis) = 24.39 Å, with two antiparallel chains per unit cell and space group P212121. The amylose chain is a left-handed 61(1.355) helix with three turns per crystallographic repeat. The O(6) rotational position is approximately gt. Dimethyl sulfoxide is located inside the helix with one DMSO molecule for every three glucose residues. An additional four DMSO molecules and eight water molecules each are located in the large interstices between chains, and it is the interaction of these molecules with the helix that results in the pseudotetragonal chain packing. The interstitial DMSO is the source of the previously reported additional layer lines, which are not consistent with the 8.13-Å amylose repeat distance. The final R factor for the layers with amylose contribution to the structure factors was 0.29, while the overall R factor was 0.35. The stereochemical packing analysis provided suitable phasing models for the subsequent X-ray refinement.
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  • 152
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    Biopolymers 13 (1974), S. 1549-1556 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dielectric dispersion of DNA was studied in the frequency range 100 Hz-100 kHz at four different temperatures (6-30°C). The dielectric increment ε0-ε∞ increased with the rise of temperature. The relaxation time, on the other hand, decreased. Both the increase in dielectric increment and the decrease in relaxation time could not be explained on the basis of the counterion polarization theory. Dipole moment was estimated from Kirkwood theory. It was found to decrease systematically with temperature. Even at 0°C there was a dipole moment of 104D.
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  • 153
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    Biopolymers 13 (1974), S. 1573-1605 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dependence of Förster long-range resonance energy transfer efficiency on the orientational freedom of donor D and acceptor A molecules attached to a macromolecular substrate is examined. The usefulness of polarized emission measurements in determining the mutual orientation as well as the degree of orientational freedom of D and A and thereby deriving maximum and minimum values for the D-A separation from the transfer efficieny is demonstrated.
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  • 154
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    Biopolymers 13 (1974), S. 1653-1659 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five human hemoglobins whose genetic relationship to one another involves one set of alleles, hemoglobins CC, SC, SS, AS, and AA, were studied in the deoxygenated form within a McBain gravimetric sorption system at 28°C. Water was used as the adsorbate at relative vapor pressures ranging from 0.11 to 0.39. The results of this study are reported and compared with a similar study on the ferric form of these same five hemoglobins. For both forms of hemoglobin studied, a slight increase was measured in the number of polar sites accessible to H2O vapor for those genotypes in which the substituent in the sixth position from the N terminus of the two β chains had a positively charged side chain, i.e., hemoglobin C. Those samples containing hemoglobin S (less soluble in the deoxy form) show an increased BET monolayer coverage in the deoxy as compared to the ferric form. For each genotype, the deoxygenated form had more polar sites accessible to H2O vapor than its ferric form. This finding is in agreement with an increase in the size of the central cavity as shown by crystallographic analysis.
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  • 155
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal denaturation of direct-mixed and reconstituted polylysine-DNA complexes in 2.5 × 10-4 M EDTA, pH 8.0 and various concentrations of NaCl has been studied. For both complexes, increasing ionic strength of the solution raises Tm, the melting temperature of free base pairs. The linear dependence of Tm on log Na+ indicates that the concept of electrostatic shielding on phosphate lattice of an infinitely long pure DNA by Na+ can be applied to short free DNA segments in a nucleoprotein. For a direct-mixed polylysine-DNA complex, the melting temperature of bound base pairs Tm′ remains constant at various ionic strengths. On the other hand, the Tm′ in a reconstituted polylysine-DNA complex is shifted to lower temperature at higher ionic strength. This phenomenon occurs for reconstituted complex with long polylysine of one thousand residues or short polylysine of one hundred residues. It is shown that such a decrease of Tm′ is not due to a reduction of coupling melting between free and bound regions in a complex when the ionic strength is raised. It is also not due to intermolecular or intramolecular change from a reconstituted to a direct-mixed complex. It is suggested that this phenomenon is due to structural change on polylysine-bound regions by ionic strength. It is suggested further that Na+ may replace water molecules and bind polylysine-bound regions in a reconstituted complex. Such a dehydration effect destabilizes these regions and lowers Tm′. This explanation is supported by circular dichroism (CD) results.
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  • 156
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Theoretical values are reported for the specific conductivity, charge carrier mobilities, and delocalized free paths in β-polyglycine using the parallel-chain pleated sheet conformation and the all-valence electron energy band structure obtained previously. The mobilities are found to be much larger along the polypeptide backbones than in the direction of the hydrogen bonds. This indicates a mechanism of conduction in which the former path is favored for electronic delocalization. The preexponential factor of the specific conductivity obtained theoretically agrees well with experimental results.
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  • 157
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    Biopolymers 13 (1974), S. 1747-1750 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism of a series of L-methionine oligopeptides [BOC-(Met)n-OMe] was examined in trifluoroethanol and hexafluoroacetone sesquihydrate. The results indicate that the trimer through the hexamer exists predominantly in disordered conformations in these solvents. An abrupt change in the CD pattern at the heptamer in trifluoroethanol suggests that L-methionine oligopeptides begin forming helices at this chain length.
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  • 158
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    Biopolymers 13 (1974), S. 1767-1776 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spin-lattice relaxation time (T1) of water adsorbed on collagen fibers was determined at six frequencies and temperatures varying from 25° to -80°C. Care was taken to eliminate the contributions to the signal of protons other than those in the adsorbed water. Quantitative calculations were made on T1 and the results were compared with the experimental data. It is suggested that a maximum of about 0.50-0.55 g water per g collagen forms a hydration layer, which cannot be frozen down to -90°C and exhibits a distribution of motional correlation times. For collagen samples containing a larger quantity of adsorbed water, the additional water molecules behave like ordinary isotropic water, having a single correlation time and a freezing temperature of about -10°C.
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  • 159
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    Biopolymers 13 (1974), S. 1821-1845 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Laser Raman spectra of the trinucleoside diphoshate ApApA and dinucleoside phosphates ApU, UpA, GpC, CpG, and GpU are reported and discussed. Assignments of conformationally sensitive frequencies are-facilitated by comparison with spectra reported here of poly(rA), poly(rC), and poly(rU) in deuterium oxide solutions. The significant spectral differences between ApU and UpA, and between GpC and CpG, reveal that the sequence isomers have nonidentical conformations in aqueous solution. In UpA at low temperature the bases are stacked and the backbone conformation is similar to that found in ordered polynucleotide structures and RNA. In ApU no base stacking can be detected and the backbone conformation differs from that found in UpA, both in the orientation of phosphodiester linkages and in the internal conformation of ribose. At the conditions employed neither ApU nor UpA exhibits base pairing in aqueous solutions. In both GpC and CpG the bases are stacked and the phosphodiester conformations are similar to those encountered for UpA and RNA. However, major differences between spectra of GpC and CpG indicate that the geometries of stacking and ribosyl conformations are different. In GpC the Raman data favor the formation of hydrogen bonded dimers containing GC pairs. Protonation of C in GpC is sufficient to eliminate the ordered conformation detected by Raman spectroscopy. Despite the ordered backbone conformation evident in GpU, this dinucleoside apparently contains neither stacked nor hydrogen bonded bases at the conditions employed here. The Raman data also confirm the stacking interactions in ApApA, poly(rA), and poly(rC) but suggest that the backbone conformation in poly(rC) differs qualitatively from that found in most ordered polynucleotide structures and is thermally more stable. The present results demonstrate the sensitivity of the Raman technique to sequence-related structural differences in oligonucleotides and provide additional spectra-structure correlations for future conformational studies of RNA by laser Raman spectroscopy.
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  • 160
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    Biopolymers 13 (1974) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 161
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 300-MHz proton nmr spectra (between 11 and 14 ppm) of a series of double-stranded deoxy oligonucleotides of known sequence have been recorded in H2O solution. These resonances have been assigned to the G—N1H and T—N3H protons of specific base pairs from an evaluation of the temperature dependence of the ring NH linewidths and from the selective ring NH chemical shift changes on actinomycin-D binding. The deoxy oligonucleotides exist predominantly in the DNA-B conformation as evaluated from antibiotic binding studies. Ring-current calculations have been utilized to evaluate the up-field shifts of the G—N1H and T—N3H protons in Watson-Crick base pairs due to the ring currents from the pyrimidine and purine rings of nearest neighbor base pairs in regular DNA-B- and RNA-A-type helices. The perturbations on these up-field ring-current contributions that arise from twisting and tilting a base pair adjacent to the ring NH under study have been evaluated and found to change the calculated chemical shift by ±0.6 ppm for twist and tilt distortions of 〈30°C in a single adjacent base pair. A knowledge of the experimentally assigned ring NH chemical shifts of specific base pairs in known sequences of double-stranded deoxy oligonucleotides coupled with the ring-current tables for the DNA-B helical structure permit the assignment of 13.6 ± 0.1 ppm and 14.6 ± 0.2 ppm for the G—N1H proton of an isolated GC base pair and the T—N3H proton of an isolated AT base pair, respectively.
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  • 162
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    Biopolymers 13 (1974), S. 29-61 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper describes the first experimental application of fluorescence correlation spectroscopy, a new method for determining chemical kinetic constants and diffusion coefficients. These quantities are measured by observing the time behaviour of the tiny concentration fluctuations which occur spontaneously in the reaction system even when it is in equilibrium. The equilibrium of the system is not disturbed during the experiment. The diffusion coefficients and chemical rate constants which determine the average time behaviour of these spontaneous fluctuations are the same as those sought by more conventional methods including temperature-jump or other perturbation techniques. The experiment consists essentially in measuring the variation with time of the number of molecules of specified reactants in a defined open volume of solution. The concentration of a reactant is measured by its fluorescence; the sample volume is defined by a focused laser beam which excites the fluorescence. The fluorescent emission fluctuates in proportion with the changes in the number of fluorescent molecules as they diffuse into and out of the sample volume and as they are created or eliminated by the chemical reactions. The number of these reactant molecules must be small to permit detection of the concentration fluctuations. Hence the sample volume is small (10-8 ml) and the concentration of the solutes is low (∼ 10-9 M). We have applied this technique to the study of two prototype systems: the simple example of pure diffusion of a single fluorescent species, rhodamine 6G, and the more interesting but more challenging example of the reaction of macromolecular DNA with the drug ethidium bromide to form a fluorescent complex. The increase of the fluorescence of the ethidium bromide upon formation of the complex permits the observation of the decay of concentration fluctuations via the chemical reaction and consequently the determination of chemical rate constants.
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  • 163
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    Biopolymers 13 (1974), S. 129-138 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The D and L copolymerizations of N-carboxy γ-benzyl glutamate anhydride (NCA) were carried out in a homogeneous solution with various D/L ratios, initiated by either n-butylamine or sodium methoxide, and were followed directly by circular dichroism (CD) to observe the behavior of the secondary structure of growing polymer molecules. In the n-butylamine system, the difference of the helical content between the righthanded and the lefthanded (Δα-helix) gradually increased as the polymerization proceeded, while in the sodium methoxide system, the Δα-helix had a tendency to decrease during the later stages of the polymerization. These results suggest a difference of the power of stereo-selection of monomer antipodes by the growing chain end between these systems, the stereoselectivity by the growing chain end in the sodium methoxide system being higher than that in the n-butylamine system.
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  • 164
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    Biopolymers 13 (1974), S. 169-183 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism of Ac-Ala-NHMe, cyclo(-Ala-Ala-), Ac-Ala-OMe, Ac-Ala-Ala-OMe, and Ac-Ala-Ala-Ala-OMe has been measured in water and in aqueous salt solutions as a function of temperature. Only cyclo(-Ala-Ala-) exhibits circular dichroism which is independent of temperature. Each of the linear derivatives of L-alanine exhibits a positive circular dichroism in the range 208-218 nm at 15°C in water. Heating reduces the intensity of the positive circular dichroism, and only Ac-Ala-OMe retains positive circular dichroism at 75°C in water. Isothermal addition of salts produces changes in the circular dichroism of linear derivatives of L-alanine which resemble those seen on heating. The relative effectiveness of the salts tested, at a concentration of 4M, is LiCl ≤ KCl = NaCl 〈 MgCl2 ≤ CaCl2 ≤ NaClO4. The circular dichroism of cyclo(-Ala-Ala-) is also affected by the salts. Extrapolation of the results obtained with Ac-Ala-OMe, Ac-Ala-Ala-OMe, and Ac-Ala-Ala-Ala-OMe to a long polypeptide with a -CH2R side chain in the L-configuration leads to the conclusion that this polypeptide should exhibit a temperature-dependent salt-sensitive positive circular dichroism between 208 and 218 nm when it exists as a statstical coil.
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  • 165
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    Biopolymers 13 (1974), S. 227-235 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heats of the conformational conversion ΔHc of polyuridylic acid (polyU) in the presence of various cations were determined using a differential scanning microcalorimeter and an isothermal mixing calorimeter. The first method yields a value of ΔHc = 5.2 kcal/mol of base pairs, the second one a value of ΔHc = 6.4 kcal/mol of base pairs. Knowing ΔHc and the maximal slope of the degree of conversion, which was determined from the temperature dependence of the absorbance of polyU solutions at 260 nm, we were able to evaluate the parameter of cooperativity σ. From the relation σ = eΔFstack/RT the stacking free energy ΔFstack could be calculated. Dividing the apparent enthalpy of conversion by the calorimetrically measured enthalpy yields the cooperative length N0 of one helical segment at the midpoint of conversion. The results show that the type of the cation has no influence on the magnitude of ΔHc, whereas the cooperativity of polyU is influenced by the various cations.
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  • 166
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    Biopolymers 13 (1974), S. 861-862 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 167
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    Biopolymers 13 (1974), S. 903-908 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Clipped autocorrelation functions for the fluctuating intensity of light scattered from dilute solutions of poly-L-lysine in 0.2 M NaBr have been observed over a wide range of time scales down to 1.83 μsec, and over a wide range of pH. Two poly-L-lysine samples of molecular weight 35,000 and 200,000, respectively, were compared to determine the extent of draining of the so-called random-coil configuration. The observed correlation functions were in general very satisfactorily represented by simple translation diffusion of single molecules. At high pH ∼10-10.4, there was evidence of considerable aggregation, but no indication whatsoever of any unusually fast component, as reported recently by Jamieson et al. for poly-L-lysine HBr in the absence of salt.A 30% rise in the diffusion coefficient to a peak at pH 10 parallels the previously reported dip in the intrinsic viscosity, and is interpreted in terms of a more compact structure in that pH region between the coil and helix extremes.
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  • 168
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation of deoxyribonucleoprotein (DNP) from calf thymus at different stages of deproteinization was studied.The dissociation of the first portion of histone produces no effect on the hydrodynamical and optical behavior of DNP particles. The conformational transition of a macromolecule was observed as soon as the ratio of protein to DNA ≤ 0.9.The effect of ionic strength on the conformation of DNP particles with high protein content was more strongly pronounced than that for DNA. On the contrary, DNP particles depleted of proteins (protein/DNA 〈 0.9) were found to be less sensitive than DNA to the variation of ionic strength. These data imply that the DNP molecules rich in proteins possess a superstructure that is destroyed as the protein/DNA ratio becomes 0.9.The data were analyzed in view of current theories on various model concepts. The most probable model to describe the DNP molecule was chosen by comparing the calculated and experimentally obtained parameters. We believe that DNP is best described as a “compressed coil,” possibly including superhelical regions.
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  • 169
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of some high-molecular-weight protenoid structures in radiofrequency cold plasma conditions are discussed. The fractionation results of the raw product and the spectrum of free and protenoid-bound amino acids are given. The uv analysis of these compounds is presented.A protein-forming mechanism that might have existed on the primitive earth is proposed.
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  • 170
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Double-stranded DNA can be readily adsorbed on mica or directly on carbon coated grids from the surface of solutions containing ethidium bromide, actinomine, or propidium diiodide. The DNA molecules are unfolded, well separated, and show a length distribution similar to molecules prepared by protein monolayer techniques.Since the intercalating dyes tested do not lead to an increased apparent diameter of the nucleic acid the method is useful for the study of nucleic acid-protein complexes. As a model, the binding of E. coli RNA polymerase to phage T7 and T3 DNA was examined under different conditions. The enzyme can easily be identified and its position along the DNA molecule can be mapped.
    Additional Material: 10 Ill.
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  • 171
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of a series of oligopeptides (from the tripeptide to the octadecapeptide) with the repeating sequence L-norvalyl-glycyl-L-proline and a polytripeptide with this sequence are reported. The oligomers were synthesized step by step using the mixed anhydride method. All the products were chemically and optically pure. The polymer was prepared by the active ester method, using the p-nitrophenyl ester as the polymerizable tripeptide derivative. Good yield of relatively high average molecular-weight polymer was obtained. In the accompanying paper conformational investigations, both in solution and in the solid state, on the oligomers and the polymer are described.
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  • 172
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(Nδ-carbobenzoxy, Nδ-benzyl-L-ornithine) (PCBLO) was prepared by the standard NCA method. PCBLO was converted into poly(Nδ-benzyl-L-ornithine) (PBLO) through decarbobenzoxylation with hydrogen bromide. The monomer Nδ-benzyl-L-ornithine was synthesized by reacting L-ornithine with benzaldehyde, followed by hydrogenation. The conformation of the two polypeptides was studied by optical rotatory dispersion and circular dichroism. PCBLO forms a right-handed helix in helix-promoting solvents. In mixed solvents of chloroform and dichloroacetic acid (DCA) it undergoes a sharp helix-coil transition at 12% (v/v) DCA at 25°C, as compared with 36% for poly(Nδ-carbobenzoxy-L-ornithine) (PCLO). Like PCLO, the helix-coil transition is “inverse,” that is, high temperature favors the helical form. PBLO is soluble in water at pH below 7 and has a “coiled” conformation. In 88% (v/v) 1-propanol above pH (apparent) 9.6 it is completely helical. In 50% 1-propanol the transition pH (apparent) is about 7.4; this compares with a pHtr of about 10 for poly-L-ornithine in the same solvent.
    Additional Material: 6 Ill.
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  • 173
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    Biopolymers 13 (1974), S. 1141-1160 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of ethidium bromide to DNA has been studied by various optical methods. From fluorescence polarization studies, and film, electric linear dichroism, and circular dichroism spectra, we propose assignments of the absorption bands of the dye, which are discussed in connection with wave-mechanical calculations recently reported.The optical activity induced in the dye absorption bands upon binding to DNA was attributed to various origins depending on the electronic transition considered. The visible absorption band displayed a circular dichroism due to the asymmetry of the binding site and independent of the amount of binding. The transition identified at 378 nm from the circular dichroism and electric dichroism observations was thought to be due to a magnetic-dipole transition. It remained constant with increasing amounts of dye bound. The main ultraviolet band showed circular dichroism characteristics corresponding to exciton interactions between dye molecules bound to neighboring sites.The electric dichroism observed for the strongly bound dye molecules indicated that the phenanthridinium ring of ethidium bromide was probably not perfectly parallel to the DNA base planes. When the amount of dye bound to DNA exceeded the maximum amount compatible with the exclusion of adjacent binding sites, the electric dichroism decreased owing to the appearance of externally bound dye molecules with no contribution to the dichroism.Sonicated DNA was used to study the lengthening of the DNA molecule upon complexation. Although the viscosity of the complexes increased with the amount of binding, the rotational diffusion coefficient measured by the electric birefringence relaxation was not detectably affected. The absence of variation in the electric birefringence with the binding indicated that the DNA base stacking remained unaltered.
    Additional Material: 7 Ill.
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  • 174
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    Biopolymers 13 (1974), S. 1205-1212 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the polymerization of phenylalanine N-carboxyanhydride (NCA) using poly(N-methyl-L-or DL-alanine) diethylamide as initiator, the polymerization rate was L-NCA ≃ D-NCA 〉 DL-NCA. This is a new type of selective polymerization and indicates the incompleteness of earlier investigations to study the asymmetrically selective polymerization without D-NCA. Neither secondary structure nor optical activity of the polymeric initiator is a reason for the selectivity. Hence the cause for the selectivity was sought in the properties of the NCA's in solution. However, the selectivity was not observed in the polymerization initiated by poly(L-phenylalanine) dimethylamide. The importance of the initiator being a secondary amine type was suggested. The experimental results are discussed on the basis of these considerations.
    Additional Material: 7 Ill.
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  • 175
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Classical potential energy calculations were performed for the dinucleoside phosphates UpA and GpC. Two widely accessible low-energy regions of conformation space were found for the ω′, ω pair. That of lowest energy contains conformations similar to helical RNA, with ω′ and ω in the vicinity of 300° and 280°, respectively. All five experimental observations of crystalline GpC, two of ApU, and the helical fragment of ApApA fall in this range. The second lowest region has ω′ and ω at about 20° and 80°, respectively, which is in the general region of one experimentally observed crystalline conformer of UpA, and the nonhelical region of ApApA.It is concluded that GpC and ApU, which were crystallized as either sodium or calcium salts, are shielded from each other in the crystal by the water of hydration and are therefore free to adopt their predicted in vacuo minimum energy helical conformations. By contrast, crystalline UpA had only 1/2 water per molecule, and was forced into higher energy conformations in order to maximize intermolecular hydrogen bonding.
    Additional Material: 6 Ill.
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  • 176
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dielectric dispersion measurements on poly-γ-benzyl-L-glutamate (PBLG) in dioxane and dioxane-dichloroacetic acid (DCA) mixtures in the frequency range 200 Hz-2 MHz were made in order to study the structure of molecular aggregates. The structure of aggregates is explained on the basis of the variation of dipole moment and relaxation time with degree of aggregation. PBLG was found to form linear head-to-tail-type aggregates in dioxane. These aggregates gradually reduce in size without loosing their α-helical structure during the process of disaggregation obtained by either adding DCA to the solution in dioxane or by heating. It was confirmed that the addition of 30 wt % DCA completely destroys the aggregation of PBLG in dioxane at 30°C. Thermal disaggregation, however, was not complete even at a temperature approaching the boiling point of the solvent.A reaction scheme for aggregation is proposed and equilibrium constants are calculated at various stages of aggregation. The enthalpy of aggregate formation is found to be -3 kcal/mol. Results of optical rotatory dispersion measurements of the helix-coil transition in this system are also presented.
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  • 177
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Zimm-Bragg parameters s and σ were determined for poly(γ-benzyl L-glutamate) (PBLG) in m-cresol and in dimethylformamide (DMF) from ORD data as a function of molecular weight. It was found that, within the temperature range between 10 and 55°C and on the average, s = 1.61 ± 0.1 and √σ = 0.04 ± 0.01 in m-cresol and s = 1.65 ± 0.05 and √σ = 0.045 ± 0.015 in DMF. The values of s in m-cresol decreased with increasing temperature, while the values of σ in the same solvent increased. This result for s suggests that PBLG in m-cresol will undergo a thermal helix-coil transition of normal type. The parameters in DMF showed no appreciable trend to vary with temperature. Aside from the difference between the two solvents, our results are consistent with existing data for various conformation-dependent properties such as light-scattering radius, intrinsic viscosity, and dipole moment, each indicating that the polypeptide chain has some flexibility in helicogenic solvents.
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  • 178
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    Biopolymers 13 (1974), S. 1391-1403 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism of double-helical nucleic acids was calculated as a function of geometry, including terms involving n → π* transitions. The “nonbonding” n or σ orbitals were of the azine type, delocalized, but concentrated at the nitrogen atoms of the purines and pyrimidines. Dynamic coupling of the magnetic moments of the n → π* transitions with the electric moments of π → π* transitions generated important terms. Mixing of electric dipole character into n → π* transitions by the static electric field perturbation of the molecule is of lesser importance. The largest contributions of n → π* transitions to the circular dichroism of double-helical nucleic acids are comparable in magnitude to the sum of π → π* terms only for geometries where the circular dichroism is weak. Using both n → π* and π → π* contributions one is able to match experimental and calculated circular dichroism spectra for DNA's over a much wider range of conditions than was possible previously.
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  • 179
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    Biopolymers 13 (1974), S. 1435-1445 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Laser Raman spectra are reported for solid films cast from a series of solutions containing mixtures of right- and left-handed α-helices of poly-γ-benzyl-L- and D-glutamate. Procedures were established for producing spectra that were reproducible in position to ±0.3 cm-1 and in relative intensity to a few percent for features of interest. Spectra for the pure L and pure D polymers were identical, as expected. Several small but definite spectral changes appear in the mixtures, reaching a maximum for the racemic 50:50 mixture. The changes are a shift of -1.4 cm-1 in the amide I peak at 1650.5 cm-1; a shift of about -5 cm-1 in the partially resolved amide III peak at 1291 cm-1; a shift of +2.5 cm-1 in the benzyl peak at 3062.5 cm-1; changes in relative intensity of as much as 50% in several regions; and the marked enhancement of several peaks, particularly that at 254 cm-1. These changes are discussed in terms of side-chain interactions in the packing of right- and left-handed helices.
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  • 180
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    Biopolymers 13 (1974), S. 1535-1548 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Self-diffusion coefficient measurements have been applied to the study of Na+, Ca++, and Sr++ in the presence of a linear acidic polysaccharide extracted from cartilage, i.e., chondroitin sulfate. A series of experimental determinations was made with and without supporting electrolytes, and an analysis of experiments involving the separation of the electrostatic interaction terms by an extension of Manning's theory produced results showing the preponderant nature of these electrostatic terms. The specificity of each type of ion or the influence of the pH can be considered merely as higher order corrections with respect to the preceding interactions. Counterion concentration ranges and pH ranges were determined, where either the alkaline-earth counterions become free and hence move with their normal diffusion rate, or these cations are associated with the polyelectrolyte molecule, thus giving a diffusion coefficient similar to that of the macromolecule, or the apparent diffusion coefficients vary between these two extreme diffusion rates as a function of the association equilibria. This variation can be expressed as a function of the linear charge density parameter ξ related to the structure of the polyelectrolyte, the value of which was determined and found in good agreement with published values.
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  • 181
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    Biopolymers 13 (1974), S. 1635-1651 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism (CD) spectrum of polyproline II (PPII) has heretofore been moderately well calculated from exciton theory only at the expense of assuming unreasonable chain conformations and accepting a conservative spectrum in the 180-250-nm region (which is not observed). We have incorporated far uv transitions in the polarizability approximation and, together with the π2π* transition, have calculated the resulting correction to the exciton model. This has been accompanied by a modified assignment of the ππ* transition in PPII, and a simultaneous calculation of the absorption and CD spectra of the α-helix, β structure, PPI, and PPII. We obtain good agreement with the observed CD spectrum of PPII in the 180-250-nm region for acceptable chain conformations. In addition, we predict a negative CD into the far uv, in agreement with recent experimental observations. Our calculations also reproduce features of the far uv CD spectrum of the α-helix, and are in agreement with the CD spectra of the β chain and PPI. The calculated CD of the unordered polypeptide chain is not significantly influenced by far uv contributions, indicating that our previous calculation is valid for such a system. These results demonstrate the importance of incorporating far uv transitions in order to achieve an adequate theoretical explanation of the CD spectra of polypeptides.
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  • 182
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    Biopolymers 13 (1974) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 183
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    Biopolymers 13 (1974), S. 1721-1729 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The intrinsic viscosity and molecular weight of several samples of polyhydroxyethylaspartamide with differing degrees of polymerization were determined and related, according to the Mark-Howink equation. The a exponent is consistent with a random-coil structure. The average unperturbed dimensions of the polymer, the dimensions in water, and the water-polymer interaction parameter were calculated according to Flory and Fox. The interaction of the polymer with water may explain its good efficacy as a plasma expander, as has previously been demonstrated in biological experiments. The behavior of the molecule in 6 M guanidine hydrochloride solution was also studied: this solvent has a very slight effect on the configuration of the polymer, in contrast with its normal effect on proteins.
    Additional Material: 8 Ill.
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  • 184
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Microcalorimetric heat capacity measurements on dilute and concentrated solutions and films of poly[d(A-T)·d(A-T)] in 2 M sodium chloride have been carried out. Values for enthalpy, entropy, and temperature of the helix-coil transition have been found to depend on the polymer concentration, and to have maxima near 20% (w/w) of polymer. The results are discussed in terms of polynucleotide hydration as one of the structure stabilizing factors.
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  • 185
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    Biopolymers 13 (1974), S. 1791-1807 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic parameters associated with the thermal decomposition of native collagen have been obtained by thermogravimetric techniques. In order to achieve this a thermogravimetric analysis was carried out in the temperature range of 25°C to about 1000°C. In this temperature range, it had been found that the differential primary weight loss curve had yielded three distinct peaks for the tendon collagen. The thermal decomposition corresponding to each peak was analyzed to retrieve its kinetic parameters. The peak temperature associated with the first peak decreased as the water content in a sample increased, while that of the second peak was independent of its hydration condition. It is believed that the first and the second peaks are, respectively, results of: (1) dissociation of water from collagen, and (2) of breaking of the collagen molecule itself. The third peak has not been easily identified so far. The activation energy and the order of water decomposition are obtained by various known methods. The results obtained by these different approaches agree reasonably well. The kinetic parameters of second and third peak are also obtained and reported here.
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  • 186
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    Biopolymers 13 (1974), S. 1859-1871 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problem of calculating detailed probability profiles giving the probability of each unit in the chain to be in the ordered state (and all other average quantities as well including the fraction of strand association) for specific-sequence macromolecules requiring statistical weights that correlate up to the total number of units in the chain (e.g., DNA, collagen) is formulated in terms of recursion relations for appropriate a priori and conditional probabilities, thus generalizing the approach of Lacombe and Simha for nearest-neighbor correlations in specific sequence macromolecules. The technique allows the probability profiles for chains of thousands of units to be calculated in minutes making no approximation in the basic model.
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  • 187
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    Biopolymers 13 (1974), S. 1909-1926 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Interaction between poly(Lys50, Tyr50) and DNA has been studied by absorption, circular dichroism (CD), and fluorescence spectroscopy and thermal denaturation in 0.001M Tris, pH 6.8. The binding of this copolypeptide to DNA results in an absorbance enhancement and fluorescence quenching on tyrosine. There is also an increase in the tyrosine CD at 230 nm. The CD of DNA above 250 nm is slightly shifted to the longer wavelength which is qualitatively similar to, but quantitatively much smaller than, that induced by polylysine binding. At physiological pH the poly(Lys50, Tyr50)-DNA complex is soluble until there is one lysine and one tyrosine per nucleotide in the complex. The same ratio of amino acid residues to nucleotide has also been observed in copolypeptide-bound regions of the complex. The addition of more poly(Lys50, Tyr50) to DNA yields a constant melting temperature, Tm′, for bound base pairs at 90°C which is close to that of polylysine-bound DNA under the same condition. The melting temperature, Tm, of free base pairs at about 60°C on the other hand, is increased by 10°C as more copolypeptide is bound to DNA. As the temperature is raised, both absorption and CD spectra of the complexes with high coverage are changed, suggesting structural alteration, perhaps deprotonation, on bound tyrosine. The results in this report also suggest that intercalation of tyrosine in DNA is unlikely to be the mode of binding.
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  • 188
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    Biopolymers 13 (1974), S. 2565-2570 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Normal vibration analysis of cyclic tetraglycine has been carried out employing the Urey-Bradley force field and the vibrational assignments are compared with those in related molecules.
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  • 189
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Um den Mechanismus der Katalyse der Polyvinylamin-Kupfer(II)-Chelate bei der Auslösung der Vinylpolymerisation zu klären, wurden die Stabilitätskonstanten dieser Chelate durch Anwendung einer modifizierten BJERRUMschen Methode gemessen, und die Konzentration der chemischen Spezies wurde auf Grund der Chelattheorie abgeschätzt. Anhand dieser Ergebnisse wurde die Aktivität der Polyvinylamin-Kupfer(II)-Chelate bei der Polymerisation von Acrylnitril und von Methylmethacrylat bei verschiedenen pH-Werten diskutiert.
    Notes: In order to clarify the mechanism of catalysis of polyvinylamine-copper(II) chelates on the initiation of vinyl polymerizations, stability constants of these chelates were measured by applying a modification of BJERRUM'S method, and each concentration of the chemical species was estimated on the basis of the chelate theory. From these results, the activity of the polyvinylamine-copper(II) chelates for the polymerization of acrylonitrile and methyl methacrylate at different pH values was discussed.
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  • 190
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Copolymerisation von 4(5)-Vinylimidazol mit γ-Vinyl-γ-butyrolacton wurde in Gegenwart von 2,2′-Azoisobutyronitril oder Benzoylperoxid durchgeführt. Die Initiatoren üben keinen Einfluß auf die Copolymerisationsparameter aus. Diese werden auch von Methanol als Lösungsmittel nicht beeinflußt. Die Copolymerisationsparameter wurden zu r1 = 20,0 ± 0,8 und r2 = 0,030 ± 0,002 bestimmt.Die katalytische Aktivität des Copolymers bei der Hydrolyse von p-Nitrophenylacetat (4) und von 3-Acetoxy-N,N,N-trimethylaniliniumjodid (5) bei pH = 8,0 war über doppelt so groß wie die eines statistischen Terpolymers mit Imidazol-, Carbonsäure- und Hydroxyl-Gruppen.
    Notes: Copolymerizations of 4(5)-vinylimidazole (1) and γ-vinyl-γ-butyrolactone (2) initiated by 2,2′-azoisobutyronitrile or benzoyl peroxide were carried out. The initiators did not affect the radical reactivity ratio (r). In addition, the reactivity ratio was not influenced by methanol as solvent. The following ratios were obtained r1 = 20,0 ± 0,8 and r2 = 0,030 ± 0,002.The catalytic activity of the copolymers in the hydrolyses of p-nitrophenyl acetate (4) and 3-acetoxy-N,N,N-trimethylanilinium iodide (5) at pH = 8,0 was found to be more than twice as high as that of a random terpolymer containing imidazole, carboxylic acid, and hydroxy moieties.
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  • 191
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Kobalt(III)-Komplexe, die einen Polymer-Liganden enthalten, cis-[Co(en)2PVPCl]Cl2, cis-[Co(trien)PVPCl]Cl2, cis-[Co(en)2PVPBr]Br2, cis-[Co(en)2PVPN3]Cl2 und cis-[Co(en)2-QPVPCl]Cl2 (PVP = Polyvinylpyridin, QPVP = teilweise quaterniertes PVP), wurden dargestellt, und ihre Reduktion mit Ferrosulfat wurde untersucht. Es wurde gezeigt, daß die Komplexbildung mit QPVP durch sterische Faktoren beeinflußt wird, wie durch den Polymerisationsgrad des Polymer-Liganden und die Raumerfüllung der Quaternierungsmittel. Die Quaternierung des Polymer-Liganden selbst zeigte jedoch nur einen geringen sterischen Einfluß auf die Reduktionskinetik. Für die verschiedenen Brückenliganden (X) ergab sich folgende Reihe in bezug auf die Reduktionsgeschwindigkeit von cis-[Co(en)2PVPX]2+:N3 〉 Cl 〉 Br. Die Reduktionsgeschwindigkeit von cis-[Co(en)2PVPCl]2+ ist größer als die von cis-[Co(trien)PVPCl]2+. Die Einflüsse der Brücken- und Nichtbrückenliganden auf die Reduktion sind ähnlich für die Polymer-Komplexe und die monomeren Analoga.
    Notes: Cobalt(III)-complexes having a polymeric ligand, cis-[Co(en)2PVPCl]Cl2, cis-[Co(trien)-PVPCl]Cl2, cis-[Co(en)2PVPBr]Br2, cis-[Co(en)2PVPN3]Cl2 and cis-[Co(en)2QPVPCl]Cl2 (where PVP = poly(4-vinylpyridine) and QPVP = partially quarternized PVP) were prepared and their reduction with ferrous sulfate was studied. Complex formation with QPVP was shown to be affected by steric factors such as the degree of polymerization and the bulkiness of the quaternizing agents, but the quarternization showed only a small steric influence on the reduction kinetics. The order of the reduction rate of cis-[Co(en)2PVPX]2+ with respect to the bridging ligand X is N3 〉 Cl 〉 Br, and the reduction rate of cis-[Co(en)2PVPCl]2+ is higher than that of cis-[Co(trien)PVPCl]2+. The effects of bridging and non-bridging ligands in the reduction of polymer complexes were the same as those for the monomeric analogues.
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  • 192
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die FLORYsche Theorie über das Prinzip der übereinstimmenden Zustände für Polymerlösungen wurde geprüft, indem die theoretisch berechneten Parameter mit experimentellen Ergebnissen verglichen wurden. Der osmotische Druck des Systems Polystyrol/Äthylmethylketon wurde für Polymerkonzentrationen zwischen 10 und 30% bei 10 bis 55°C gemessen. Unter Verwendung der Parameter X12 und Q12, die den erhaltenen Daten am besten entsprachen, wurden die berechneten Parameter mit den experimentellen Ergebnissen verglichen. Der Entropie-Parameter ψ1 sowie der Enthalpie-Parameter χH, 1 waren negativ und nahmen mit steigender Temperatur ab. Mit Hilfe der anpassungsfähigen Parameter X12 und Q12 gibt die FLORYsche Theorie die thermodynamischen Größen ziemlich gut wieder, obwohl eine geringe Abweichung von den experimentellen Ergebnissen zu bestehen scheint. Die SHULTZ-FLORYsche Methode zur Bestimmung der Theta;-Temperatur wurde auf der Grundlage dieser Theorie diskutiert.
    Notes: The polymer solution theory on the corresponding state principle developed by FLORY was examined by comparing the thermodynamic parameters calculated theoretically with experimental results. The osmotic pressure of the polystyrene/ethyl methyl ketone system was determined for solutions of polymer concentrations 10 to 30% at 10 to 55°C. Using X12 and Q12 parameters best fitting to these data, the calculated parameters were compared with experimental results. Both the entropy parameter ψ1 and enthalpy parameter χH, 1 were negative and decreased with increasing temperature. FLORY'S theory elucidates appreciably well the thermodynamic quantities with the use of the adjustable parameters X12 and Q12, but there seems to remain still some disagreement with experimental results. SHULTZ-FLORY'S method for determining the Θ-temperature was discussed based on this theory.
    Additional Material: 7 Ill.
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  • 193
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurde der Einfluß der sterischen Hinderung durch Polypeptid-Seitenketten auf den Wachstumsmechanismus von Polypeptidkristallen während der Polymerisation untersucht. Dabei wurden von uns Untersuchungen der Kinetik der heterogenen Polymerisation von L-Valin-LEUCHS-Anhydrid (NCA), L-Isoleucin-NCA und L-Leucin-NCA mit Butylamin als Initiator in Acetonitril und der Strukturen sowie der Morphologie der gebildeten Polymere durchgeführt. In den Anfangsstadien der Polymerisation bildeten sich Oligomere, die in dünnen, bandförmigen Kristallen mit antiparalleler β-Konformation kristallisierten. Die molekularen Anordnungen in den Kristallen wurden mit Hilfe der Elektronenbeugung untersucht. In den späteren Stadien der Polymerisation setzten die gewachsenen Poly(L-valin)- und Poly-(L-iso1eucin)-Ketten die β-Struktur weiter fort, und ihre aktiven Enden wurden in den gebildeten Kristallen eingeschlossen, was ein-Einpendeln des Umsatzes bei einem niedrigen Wert zur Folge hatte. Poly(L-leucin) andererseits schien Kristalle mit gestreckten Ketten zu bilden, die zu einem sehr hohen Umsatz führten. Dies kann nicht ohne die Annahme erklärt werden, daß sich auf den in den Anfangsstadien der Polymerisation gebildeten β-Skelettkristallen α-Helix-Ketten bilden, wie dies im Falle des Poly(L-alanins) bereits früher berichtet wurde.
    Notes: In order to examine the effect of the steric hindrance by the polypeptide side chains on the growth mechanism of polypeptide crystals in the course of polymerization, we studied kinetics of the heterogeneous polymerization of L-valine N-carboxy anhydride (NCA), L-isoleucine NCA, and L-leucine NCA initiated by butylamine in acetonitrile and the structures and morphologies of the resultant polymers. In the early stages of polymerization, oligomers formed crystallized into thin ribbon-like crystals with the antiparallel β-conformation. The molecular arrangements in the crystals were studied by electron diffractions. In the later stages, the grown chains of poly(L-valine) and poly(L-isoleucine) continued to take the β-structure and their active ends were occluded in the crystals formed, which resulted in the levelling off of the conversion at a low value. On the other hand, poly(L-leucine) seemed to give the extended chain crystal, which made the conversion very high. This can not be accounted for without assuming the formation of β-helical chains onto the β-skeleton crystals formed in the early stages of polymerization as in the case of poly(L-alanine) reported previously.
    Additional Material: 20 Ill.
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  • 194
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The kinetics and the mechanism of the mechanochemical polycondensation process of poly(oxyethyleneoxyterephthaloyl) [poly(ethylene terephthalate)] with aliphatic diamines (ethylene- and hexamethylenediamine) were studied. First order kinetics was found and in addition the fact that a very small thermal activation energy is needed and that the diamines can react as radical acceptors.
    Notes: Kinetik und Mechanismus des mechanochemischen Polykondensationsvorganges von Poly(oxyäthylenoxyterephthaloyl) (Polyäthylenterephthalat) mit aliphatischen Diaminen (äthylen- und Hexamethylendiamin) wurden untersucht. Es wurde gefunden, daß die Reaktion nach einer Kinetik erster Ordnung abläuft, daß eine äußerst geringe thermische Aktivierungsenergie benötigt wird und daß die Diamine als Radikalakzeptoren auftreten können.
    Additional Material: 17 Ill.
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  • 195
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zur Aufklärung des Mechanismus der Redox-Polymerisation von Methylmethacrylat, die die Redox-Startsysteme N-Halogendiäthylamin + Fe2+ und Triäthylamin + Halogen + Fe2+ in wäßrigem Medium unter Lichtausschluß bewirken, wurden die Endgruppen des Polymeren nach der Farbstoff-Verteilungsmethode untersucht. Im Falle von Chlor als Halogen kommt es mit beiden Startsystemen lediglich zum Einbau von Aminogruppen in das Polymere in einem Ausmaß von ca. 1 Endgruppe pro Polymermolekül. Bei Verwendung des Startsystems Triäthylamin + Halogen + Fe2+ liegen darüber hinaus die in das Polymer eingebauten Aminogruppen zu einem großen Teil in quaternärer Form vor. Mit Brom als Halogen findet bei beiden Anregungssystemen lediglich ein Bromeinbau, nicht jedoch ein Einbau von Aminogruppen in das Polymere statt. Die Chlor enthaltenden Startsysteme haben sich für die Herstellung von solchen Polymeren nützlich erwiesen, die eine Aminogruppe nur an einem der beiden Kettenenden besitzen sollen.
    Notes: The mechanism of the redox polymerization of methyl methacrylate in aqueous medium in the dark was studied for the redox initiator systems N-halodiethylamine + Fe(II) and triethylamine + halogen + Fe(II), by analysis of the polymer end groups using the dye partition method. In the case of chlorine, both these initiator systems incorporate only the amino group into the polymer to an extent of about one group per polymer molecule. The polymers are found to be free from chlorine. Furthermore, a large portion of the total amino groups introduced into the polymer, using the initiator system triethylamine + halogen + Fe(II) are quaternary in nature. In the case of bromine, both the initiator systems introduce only a bromine atom and no amino group into the polymer. The initiator systems containing chlorine prove to be useful for the preparation of polymers containing amino groups at the one end only.
    Additional Material: 3 Ill.
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  • 196
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die radikalische Polymerisation des Divinylketons in Aceton bei 50°C wurde untersucht und mit den Resultaten bereits bekannter radikalischer Polymerisationen anderer 1,4-Diene vergl+hen. Es wird gezeigt, daß Divinylketon einer bicyclischen Cyclopolymerisation unterliegt, die derjenigen des Divinyläthers und des Divinylsulfids ähnlich ist. Die Cyclisierungskonstanten werden ermittelt und die Zusammensetzung der Polymere (als lineare, monocyclische und bicyclische Struktureinheiten) als Funktion der Monomerkonzentration, bei welcher die Polymerisation durchgeführt wurde, berechnet.
    Notes: The free radical polymerization of divinyl ketone at 50°C in acetone solutions was investigated. The results are compared with those already reported for the free radical polymerization of other 1,4-dienes. It is shown that divinyl ketone undergoes bicyclic cyclopolymerization in a similar way as divinyl ether and divinyl sulfide. The cyclization ratios are computed and the polymer composition, in terms of linear, monocyclic and bicyclic structural units, is calculated as a function of the monomer concentration at which the polymerization was carried out.
    Additional Material: 3 Ill.
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  • 197
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 175 (1974), S. 467-481 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The oxidation of molten foils (20μm) from high pressure polyethylene at 157°C and at 650 Torr (= 867 mbar) oxygen pressure was studied and kinetically analyzed for the period of maximum rate.The oxygen uptake, weight increase, and hydroperoxide formation start with a rate different from zero; the initial rate of carbonyl groups and volatile products is practically zero.The absorbed oxygen, except in the initial stage, shows a distribution of the ratio 1:1 between the polymer (predominantly as carbonyl groups) and volatile products (such as water). The average number of C-atoms in the volatile fragments was estimated from kinetic data to be 6 per O-atom.
    Notes: Die Oxidation von geschmolzenen Folien (20μm) aus Hochdruckpolyäthylen wurde bei 157°C und 650 Torr (= 867 mbar) Sauerstoffdruck untersucht und kinetisch in der Periode der maximalen Geschwindigkeit ausgewertet.Die Sauerstoffaufnahme, die Gewichtszunahme und die Hydroperoxidbildung beginnen mit einer von Null abweichenden Geschwindigkeit; die Anfangsgeschwindigkeit der Bildung von Carbonylgruppen und flüchtigen Produkten ist praktisch Null.Der absorbierte Sauerstoff verteilt sich außer im Anfangsverlauf im Verhältnis 1:1 zwischen dem Polymeren (vorwiegend als Carbonylgruppe) und den flüchtigen Produkten (in Form von Wasser). Die durchschnittliche Anzahl von C-Atomen in den flüchtigen Fragmenten wurde aus kinetischen Daten auf 6 pro O-Atom abgeschätzt.
    Additional Material: 8 Ill.
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  • 198
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 175 (1974), S. 523-534 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Nicht-neutralisierte und neutralisierte, syndiotaktische Poly(methacrylsäure) wird mit Diazomethan partiell verestert. Umsatz und Triadenverteilung der entstenhenden cosyndiotaktischen Methylmethacrylat-Methacrylsäure-Copolymeren und deren Fraktionen werden durch 1H-NMR-Spektroskopie bestimmt. Nicht-neutralisierte Poly(methacrylsäure) ergibt Copolymere, die in bezug auf den Umsatz heterogen sind; ihre Fraktionen zeigen näherungsweise eine BERNOULLI-Verteilung der Triaden. Neutralisierte Poly(methacrylsäure) liefert hingegen homogene Copolymere mit einer innerhalb der Meßgenauigkeit liegenden BERNOULLI-Verteilung der Triaden. Ein kinetischer Nachbargruppeneffekt tritt daher bei der Veresterung mit Diazomethan nicht auf. So hergestellte Copolymere weisen eine einfache konfigurative und kompositive Statistik auf, wie sie durch Copolymerisation der Monomeren bislang nicht hergestellt werden kann. Der Polyelektrolytcharakter der Copolymeren kann durch anschließende, vollständige Veresterung mit einem zweiten Diazoalkan eliminiert werden; die Statistik der so entstehendenen Copolymeren ist mit der der ursprünglichen Copolymeren identisch.
    Notes: Syndiotactic poly(methacrylic acid) is partially esterified as such or in its neutralized form with diazomethane. The extent of reaction and the triad distribution of the resulting cosyndiotactic methyl methacrylate-methacrylic acid copolymers and their fractions are determined by 1H-NMR spectroscopy. Unneutralized poly(methacrylic acid) yields copolymers which are heterogeneous with respect to conversion, the fractions of the copolymers possessing an approximate BERNOULLIan triad distribution. Neutralized poly(methacrylic acid) results in homogeneous copolymers whose triad distribution is BERNOULLIan within accuracy of measurement. A kinetic neighboring group effect is therefore not operative during the esterification with diazomethane. Copolymers may thus be prepared which are of simple configurational and compositional statistics, not obtainable at present by copolymerization of monomers. The polyelectrolyte character of the copolymers may be eliminated by consecutive, complete esterification with a second diazoalkane, the statistics of the derived copolymers being identical with that of the precursor copolymers.
    Additional Material: 6 Ill.
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  • 199
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Bildung von Polyionen-Komplexen in wäßrigem Medium zwischen Polykationen, die Ladungen in der Kette tragen, und Polycarbonsäuren, wie Polymethacrylsäure (PMAA), Polyacrylsäure (PAA) und Polyitaconsäure (PIA), wurde untersucht. Es wurde gefunden, daß die Polykationen stabilere Komplexe bilden als die entsprechenden niedermolekularen Kationen und daß neben der Kettenlänge die Dissoziationskonstanten und die Hydrophobie die Bildungsfähigkeit der Polyionen-Komplexe beeinflußte. Die Zusammensetzung der Komplexe zwischen Polykationen und Polycarbonsäuren wurde vor allem durch den Dissoziationsgrad (α′) der Polycarbonsäuren bestimmt.Aus diesen Ergebnissen ist zu schließen, daß die Komplexe durch die kooperativen Wechselwirkungen zwischen zwei Polymerketten, die entgegengesetzte Ladungen tragen, gebildet werden und daß die Polyionen-Komplexe reversibel Schleifen-, Leiter- und dazwischenliegende Strukturen ausbilden.
    Notes: The formation of polyion complexes in aqueous medium between polycations carrying charges in the chain backbone and poly(carboxylic acid)s, such as poly(methacrylic acid) (PMAA), poly(carboxylic acid) (PAA), and poly(itaconic acid) (PIA), were studied. It was found that polycations formed more stable complexes than their corresponding low molecular weight cations and that in addition to the chain length, dissociation constants and the hydrophobicity dominated the ability of the formation of a polyion complex. The compositions of the complexes between polycation and polycarboxylic acid were defined mainly by the degree of dissociation (α′) of the poly(carboxylic acid).From these results it is concluded that the complexes are formed by the cooperative interactions between two polymer chains which have charges of opposite sign and the structures of polyion complexes can accept reversible states like loops, ladders, and their intermediate shapes.
    Additional Material: 6 Ill.
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  • 200
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 175 (1974), S. 641-654 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird gezeigt, daß die zur Zeit vorhandenen Kenntnisse über die Struktur von amorphen Blockpolymeren mit der Vorstellung von der Existenz eines beträchtlichen Anteils an Nahordnung der Kettensegmente übereinstimmen. Es wird vermutet, daß die starke Veränderung der Molekulargewichtsabhängigkeit der NEWTONschen Viskosität von Polymerenschmelzen beim Erreichen eines kritischen Molekulargewichts Mc für die Bildung von „Verhakungen“ hauptsächlich bedingt ist durch den übergang von Makromolekülen aus der gestreckten Konformation in eine solche mit statistischen Faltungen der Makromoleküle. Schließlich werden empirische Abhängigkeiten ermittelt, welche die Werte der Packungskoeffizienten eines Polymeren im kristallinen Zustand sowie die „besten“ numerischen Werte von Mc mit molekularen Parametern eines Polymeren verbinden.
    Notes: It is shown that the presently available information on the structure of bulk amorphous polymers is consistent with the concept of the existence of a substantial amount of short-range segmental order. It is suggested that the sharp change of molecular-weight dependence of NEWTONian viscosity of polymer melts with the approach to the critical “entanglement” molecular weight Mc is brought about mainly by the transition from the extended-chain conformation of the macromolecules into the statistically folded-chain conformation. Finally, empirical relationships are obtained which relate the values of polymer packing coefficients in the crystalline state as well as the “best” numerical values of Mc with molecular parameters of a polymer.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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