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  • 1985-1989
  • 1965-1969  (4,764)
  • 1967  (4,764)
  • Chemistry  (4,755)
  • Cricetulus griseus  (9)
  • 1
    ISSN: 1432-0428
    Keywords: Spontaneous Diabetes ; Chinese hamster ; Cricetulus griseus ; Clinical diabetes ; Glucose metabolism ; Leucine metabolism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons étudié cliniquement le diabète héréditaire du hamster chinois, et, en particulier, nous avons pu suivre 79 animaux pendant des périodes prolongées. Le diabète chez ce hamster est variable quant à sa sévérité et quant à son évolution clinique. Par plusieurs aspects il ressemble au diabète humain, mais il s'en différencie par l'énorme volume urinaire, la fréquence du diabète léger même chez les animaux jeunes, une résistance relative à l'insuline, et une capacité extraordinaire de compensation pour les pertes de liquide et de glucose dans l'urine. Ces différences sont si marquées qu'elles suggèrent l'existence de différences fondamentales entre le métabolisme du hamster chinois et celui de l'homme. Bien que certaines différences aient pu être démontrées dans le métabolisme du glucose et de la leucine entre l'animal diabétique et l'animal normal, la signification statistique de ces différences reste à établir.
    Abstract: Zusammenfassung Eine klinische Untersuchung des hereditären Diabetes im chinesischen Hamster hat ergeben, daß große Schwankungen in bezug auf die Schwere und den Verlauf der Stoffwechselstörung bestehen. Verschiedene Merkmale der Krankheit in diesem Tier ähneln dem menschlichen Diabetes, während andere Aspekte, wie z.B. Urinmenge und Glykosurie, oder die beträchtliche Anzahl der Tiere mit leichtem jugendlichen Diabetes, der hohe Insulinbedarf und die Fähigkeit größere Urinund Glucoseverluste auszugleichen, darauf hinweisen, daß diese Widersprüche artbedingt sein könnten.In vivo undin vitro durchgeführte Stoffwechselstudien mit Glucose und Leuzin scheinen im normalen und diabetischen Tier leicht zu differieren, obgleich dies statistisch nicht zu beweisen war.
    Notes: Summary A clinical study of hereditary diabetes in the Chinese hamster has revealed a great variety in severity and course of the disease. Several aspects of the disease in this animal resemble human diabetes, whereas other parameters, such as gross urine volumes and glycosuria, a considerable number of mild juvenile-onset diabetics, high insulin requirement, and ability to compensate for urine losses of fluids and glucose would indicate that species differences in metabolism may be the cause of these discrepancies. — Metabolismin vivo andin vitro of glucose and leucine appears to be slightly different in the normal and diabetic animal, although statistically this has not been proven.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 74-84 
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese Hamster ; Cricetulus griseus ; Insulin in Plasma ; Insulin in pancreas ; Pancreas ; Free fatty acids ; Detection of diabetes ; Muscle metabolism ; Adipose tissue metabolism ; Liver glycogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons dépisté le diabète chez le hamster chinois par des dosages qualitatifs de la glucosurie. Nous avons ensuite caractérisé chaque cas par la mesure quantitative du glucose urinaire, par des surcharges au glucose et par le dosage de la glycémie à jeun et non à jeun, des corps cétoniques, des acides gras libres (AGL) plasmatiques, de l'insuline plasmatique et pancréatique, et des taux hépatiques de glycogène. En outre, nous avons mesuré l'utilisation du glucose par le diaphragme et le tissu adipeux épididymaire, avec et sans stimulation par l'insuline. Les animaux nécessitant l'administration d'insuline ont reçu leur dernière injection au moins 24 heures avant chaque étude. Les taux de glucose dans l'urine ont varié entre 51 et 1600 mg par 24 heures. Le test de surcharge au glucose s'est révélé nettement anormal chez les animaux diabétiques, la surcharge étant de 250 mg de glucose par kg de poids. Chez les diabétiques, la glycémie après surcharge est fortement variable, contrairement à l'uniformité de la réponse observée chez les non-diabétiques. Le glycogène hépatique à jeun est de 3, 1±1,0% pour les diabétiques, et de 0,4±0,7% de poids frais d'organes pour les non-diabétiques. Les taux plasmatiques des AGL et des corps cétoniques sont manifestement élevés chez les hamsters chinois diabétiques et cétosiques alors que le contenu en insuline du plasma et du pancréas est abaissé de façon marquée. Ceci n'a pas été observé chez les diabétiques moins sévères qui se rapprochent des non-diabétiques. Les AGL plasmatiques sont élevés chez tous les hamsters chinois (moyenne pour les non-diabétiques 1800μE/l, pour les diabétiques sévères 2800μE/l) Les taux d'AGL sont les mêmes à jeun et non à jeun chez les animaux non-diabétiques ou souffrant d'un diabète léger. L'utilisation du glucose par le muscle et le tissu adipeux du hamster diabétique ne diffère pas significativement de celle des tissus non-diabétiques et leur stimulation par l'insuline est semblable. L'insuline immunoréactive des hamsters traités à l'insuline reste élevée dans le plasma pendant plus de 26 jours après la dernière injection. — Ces observations semblent indiquer que le pancréas des hamsters chinois diabétiques sécrète plus difficilement de l'insuline en réponse à une stimulation par le glucose. Les taux normaux d'insuline plasmatique chez les hamsters avec un diabète léger, mais présentant pourtant une nette glucosurie, une hyperglycémie et une réponse anormale à la surcharge en glucose, suggèrent l'existence d'une interférence avec l'action normale de l'insuline et peut-être une augmentation de la production de glucose par le foie.
    Abstract: Zusammenfassung Beim chinesischen Hamster wurde der Diabetes durch qualitative Urinuntersuchungen auf Glucose aufgespürt. Es wurde dann jeder Fall näher charakterisiert durch quantitative Uringlucosebestimmungen, Glucosebelastungsproben und Messungen von Nüchtern- und Nichtnüchternwerten für Blutzucker, Blutketonkörper, freie Fettsäuren (FFS) und Insulin im Plasma, von Insulin im Pankreas, und von Nüchternwerten für Leberglykogen. Außerdem wurde der Glucoseverbrauch des Zwerchfells und des epididymalen Fettgewebes sowie mit, als auch ohne Insulin gemessen. Diejenigen Tiere, die Insulin erforderten, erhielten ihre letzte Injektion 24 Stunden vor dem Versuch. Glucosurie schwankte zwischen 51 und 1600 mg/24 Std. Bei einer Belastung von 250 mg/kg wiesen die diabetischen Tiere eine wesentlich verminderte Glucosetoleranz auf. Sie sprachen sehr unterschiedlich auf die Glucosebelastung an, während die nichtdiabetischen Tiere in ihrer Reaktion einheitlich waren. — Im Vergleich zu den nichtdiabetischen Hamstern, wo die Mittelwerte für Nüchternleberglykogen bei 0.4±0.7 Prozent des Frischlebergewichtes lagen, hatten die diabetischen Tiere einen Glykogengehalt der Leber von 3.1±1.0 Prozent. — Chinesische Hamster mit schwerem Diabetes haben deutlich erhöhte FFS-Werte und Ketonkörper, sowie einen wesentlich niedrigeren Plasma- und Pankreasinsulinspiegel. Bei Tieren mit leichter Diabetes hingegen sind diese Untersuchungen, im Vergleich zu den Kontrolltieren, unverändert. Alle chinesischen Hamster haben hohe Plasma-FFS-Werte (nichtdiabetische 1800μE/L, schwer diabetische 2800μE/L). Nüchtern- und Nichtnüchternwerte für FSS sind beim leicht diabetischen oder gesunden Tier etwa gleich hoch. Der Glucoseabbau durch Muskel- und Fettgewebe des diabetischen und nichtdiabetischen Hamsters unterscheidet sich nicht sehr, und beide Gruppen sprechen ungefähr gleich stark auf Insulinstimulierung an. Das im Plasma der insulinbehandelten Tiere vorkommende immunreaktive Insulin ist noch 26 Tage nach der letzten Injektion nachweisbar. — Diese Ergebnisse lassen vermuten, daß der Pankreas des diabetischen Hamsters nur schwerlich in der Lage ist, nach einer Glucosestimulierung Insulin auszuschütten. Die Beobachtung, daß der Plasma-Insulinspiegel im leichten Diabetes normal ist, diese Tiere jedoch Glucosurie, Hyperglykämie und abnormale Glucosetoleranz aufweisen, führt zu der Annahme, daß ein leichter Diabetes beim chinesischen Hamster eine Beeinträchtigung der Insulinwirkung mit sich bringen, und Ursache einer vermehrten Glucoseproduktion durch die Leber sein kann.
    Notes: Summary Diabetes in Chinese hamster was initially detected by qualitative tests for urine glucose. The disease was characterized by quantitating urine glucose, glucose tolerance tests and measurement of fasting and nonfasting blood sugar, blood ketones, plasma free fatty acids (FFA), plasma insulin, pancreatic insulin and fasting levels of liver glycogen. In addition, basal levels of glucose utilization by diaphragms and epididymal adipose tissue and the response of these tissues to insulin was measured. Those animals requiring insulin received their last injection 24 hours prior to study. Glucosuria varied from 51 to 1600 mg/24 hours. Diabetics had significantly decreased tolerance to a 250 mg/kg glucose load. The response varied considerably in diabetics but was uniform in the nondiabetics. Diabetics had mean fasting liver glycogen levels of 3.1±1.0 compared with 0.4± 0.7 percent of fresh liver weight for nondiabetics. Severely ketotic, diabetic Chinese hamsters had significantly elevated FFA and ketone levels and significantly lower plasma and pancreatic insulin levels but mild diabetics did not differ from controls with respect to these parameters. All Chinese hamsters had high plasma FFA levels (nondiabetics 1800μE/l, severe diabetics 2800μE/l. Fasting and nonfasting FFA levels did not differ in mild diabetic and nondiabetic animals. Muscle and adipose tissues from diabetic hamsters had basal rates similar to nondiabetics and had similar responses to insulin. Hamsters maintained on insulin had greatly elevated immunoreactive insulin levels in their plasma, which persisted for 26 days. — The data suggest that severely diabetic hamsters may have a decreased ability of the pancreas to secrete insulin in response to a glucose stimulus. The observations that plasma insulin levels are normal in mild diabetics but that these animals have glucosuria, hyperglycemia and abnormal glucose tolerance suggest that mild diabetes in the Chinese hamster may involve interference with insulin action and/or increased hepatic glucose output.
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  • 3
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese hamster ; Cricetulus griseus ; Pancreas in vitro ; Insulin secretion in vitro ; Insulin secretion in diabetes ; Prediabetes ; Preclinical diabetes ; Antibodies to insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons mesuré la sécrétion d'insuline du tissu pancréatiquein vitro en présence de glucose chez 22 hamsters chinois normaux, 6 diabétiques et 8 ayant montré une glucosurie intermittente. Les valeurs obtenues ont été comparées avec l'hyperglycémie et l'insulinémie de ces mêmes animaux avant leur mort. Nous avons observé que la sécrétion insuliniquein vitro était proportionnelle au contenu en insuline du pancréas et au quotient de l'insulinémie divisée par le glucose plasmatique indépendamment de l'état métabolique de l'animal. Pourtant, la sécrétion insuliniquein vitro la plus basse a été observée chez les animaux diabétiques, et la plus élevée chez ceux qui avaient présenté une glucosurie intermittente. La relation possible de ces observations avec les théories actuelles du »pré-diabète« est discutée.
    Abstract: Zusammenfassung Die durch Glucose stimulierte Insulinsekretion wurdein vitro am Pankreasgewebe chinesischer Hamster gemessen und mit den Glucose- und Insulin-Plasmaspiegeln derselben Tierein vivo, sowie mit der Granulierung derer Inselzellen (22 normale, 6 diabetische und 8 zeitweise glykosurischer chinesischer Hamster) verglichen. Es bestand eine direkte Korrelation zwischen Insulinsekretion und Insulingehalt des Pankreas, sowie mit dem Verhältnis Insulin/Glucose im Plasma, ohne Rücksicht auf den Stoffwechsel-Zustand der Tiere. Die niedrigsten Werte wurden allerdings bei den diabetischen Tieren, und die höchstens bei denjenigen mit zeitweiser Glykosurie beobachtet. Die Bedeutung dieser Resultate in bezug auf bestehende Theorien des „Pre Diabetes“ wird diskutiert.
    Notes: Summary Insulin secretion by pancreatic tissuein vitro in response to glucose was related to plasma glucose and plasma insulin levels during life, and to the degree of granulation of the islets of Langerhans in 22 normal, 6 diabetic and 8 intermittently glycosuric Chinese Hamsters. Secretion was directly related to the insulin content of the pancreas and to the ratio of insulin to glucose in plasma, irrespective of the metabolic state of the animal, but was lowest in diabetic animals and highest in those with intermittent glycosuria. The relevance of these findings to current theories concerning “prediabetes” is discussed.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 115-123 
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese hamster ; Cricetulus griseus ; Liver in vitro ; Diaphragm in vitro ; Heart in vitro ; Kidney in vitro ; Adipose tissue in vitro ; Glucose metabolism in vitro ; Pyruvate metabolism ; Bicarbonate metabolism ; Microangiopathy ; Prediabetes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons étudié le foie, le diaphragme, le coeur, le rein et le tissu adipeux de 5 hamsters chinois avec diabète plus ou moins sévère, en incubant ce tissuin vitro avec du glucose uniformément marqué au14C, ou marqué en positions 1-, 2-, ou 6-, avec du pyruvate-2-14C, ou avec du bicarbonate-14C, diversement combinés. Nous avons également examiné au microscope électronique le pancréas et le rein de ces animaux. Nous n'avons pas trouvé d'indication histologique d'hypertrophie des îlots pancréatiques, le contenu en insuline du pancréas étant diminué et l'insuline plasmatique relativement diminuée également. Nous n'avons pas non plus trouvé régulièrement une microangiopathie des capillaires des îlots. Lefoie de hamsters diabétiques de type sévère ou léger incorpore moins les carbones du glucose et du pyruvate dans le CO2, le glycogène et les acides gras. De même, lemuscle des animaux avec un diabète sévère oxyde moins de glucose en CO2. Par contre, letissu adipeux des animaux diabétiques ne se distingue pas de celui d'animaux normaux, peut-être à l'exception d'une diminution d'activité du cycle des pentoses. Letissu rénal des hamsters diabétiques incorpore moins de carbbone-2 du pyruvate dans le CO2, mais son comportement est par ailleurs normal. Une réponse à l'insuline a été observéein vitro tant pour le muscle que pour le tissu adipeux, alors que les concentrations d'insuline employées étaient élevées. Malgré le petit nombre de hamsters étudiés, il est permis de conclure que ces altérations sont comparables à celles déjà observées chez des rats souffrant d'une carence insulinique chronique expérimentale. Bien qu'il ne soit pas possible d'exclure qu'il y ait eu une première phase transitoire et non détectée, caractérisée par une hypersécrétion insulinique, nous pensons plutôt que nos observations dans ce petit groupe d'animaux diabétiques sont apparentées à celles faites préalablement chez des rats avec déficience chronique en insuline induite expérimentalement.
    Abstract: Zusammenfassung Leber, Zwerchfell, Herz, Niere und Fettgewebe von 5 chinesischen Hamstern mit Diabetes verschiedenen Schweregrades wurdenin vitro inkubiert. Glucose-U, 1-, 2-, oder 6-14C, Pyruvat-2-14C und Bicarbonat-14C wurden in verschiedenen Kombinationen als Substrat verwandt. Pankreas und Niere wurden elektronenmikroskopisch untersucht. Eine Hypertrohpie der Pankreasinseln war histologisch nicht nachweisbar. Extrahierbares Insulin war vermindert und Plasma-Insulinwerte verhältnismäßig niedrig. Eine regelmäßige Mikroangiopathie der Inselkapillaren konnte nicht beobachtet werden. Sowohl die leicht- als auch die schwer-diabetischen Hamster zeigten einen verminderten Einbau von Glucose- sowie von Pyruvat-Kohlenstoff in CO2, Glykogen und Fettsäuren durch dieLeber. Eine herabgesetzte Oxydation von Glucose zu CO2 durch denMuskel war zumindest in schwer-diabetischen Tieren nachweisbar. Der Stoffwechsel desFettgewebes war durch den Diabetes nicht beeinflußt; die Aktivität des Pentosezyklus war möglicherweise herabgesetzt. DasNierengewebe des diabetischen Hamsters zeigte einen geringeren Einbau vom C-2 des Pyruvats in CO2, jedoch konnten sonst keine biochemischen Veränderungen festgestellt werden. Muskel- und Fettegewebe sprachen imin vitro Versuch auf relativ hohe Insulinkonzentrationen gut an. Die Resultate, die wir aus den Untersuchungen einer begrenzten Anzahl von Hamstern erhielten, entsprechen somit früheren Beobachtungen bei Ratten mit experimentell bedingtem chronischen Insulinmangel. Es besteht allerdings die Möglickeit, daß uns eine vorübergehende frühere Phase mit Hypersekretion von Insulin unbemerkt entging.
    Notes: Summary Liver, diaphragm, heart, kidney, and adipose tissue of five Chinese hamsters with diabetes of varying severity have been studied by incubationin vitro with glucose-U-, 1-, 2-, or 6-14C, pyruvate-2-14C, and bicarbonate-14C in various combinations. The pancreas and kidney were examined by electron microscopy. There was no histologic evidence of hypertrophy of the pancreatic islets; extractable insulin was reduced, and plasma insulin was relatively reduced. There was no consistent microangiopathy of insular capillaries. Both the mild and severely diabetic hamsters had a reduction in the incorporation of the carbons of glucose and of pyruvate into CO2, glycogen, and fatty acids in theliver, and, at least in severely diabetic animals, of oxidation of glucose to CO2 in muscle. There was no change consequent to diabetes in the metabolism ofadipose tissue, except for a possible decrease in pentose cycle activity. Thekidneys of the diabetic hamsters had less incorporation of carbon-2 of pyruvate into CO2, but otherwise no biochemical changes were evident. Both muscle and adipose tissue were responsivein vitro to insulin when tested with greater physiologic amounts. While the possibility cannot be excluded that a transient earlier phase with hypersecretion of insulin escaped detection, the changes in this limited number of diabetic hamsters parallel those previously found in rats with experimental chronic deficiency of insulin.
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  • 5
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese hamster ; Cricetulus griseus ; Ultrastructure ; Pancreas ; Beta cells ; Islets ; Alpha cells ; Nerve endings in pancreas ; Glycogen ; Basement membrane ; Capillaries
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons examiné au microscope électronique les îlots de Langerhans de 15 hamsters chinois dont 7 étaient diabétiques et 8 étaient non-diabétiques, provenant soit des mêmes nichées, soit sans lien de parenté, mais concordant quant au sexe et à l'âge. Chez les animaux de contrôle, les cellulesβ prédominent et sont riches en granules, formés de vésicules de différentes tailles avec un contenu légèrement granulaire ou homogène. Dans de rares vésicules, on observe un noyau dense ou une barre centrale irrégulière et dense. Les granulations des cellulesα sont uniformément rondes, très denses et limitées par des membranes; elles sont assez clairsemées à l'exception de la périphérie des îlots. Au début du diabète, les cellulesβ sont abondantes mais, soit dégranulées, soit en voie d'infiltration glycogénique. Plus tardivement dans la maladie, les îlots ne contiennent presque que des cellulesα, les cellulesβ ayant graduellement disparu.
    Abstract: Zusammenfassung Die Langerhans'schen Inseln von 15 chinesischen Hamstern (7 diabetischen und 8 entweder verwandten oder nicht verwandten Kontrolltieren gleichen Geschlechts und Alters) wurden elektronenmikroskopisch untersucht. In den Kontrolltieren überwiegen dieβ-Zellen die reich an Granula sind. Die meisten davon sind Bläschen verschiedener Größe mit einem blassen, körnigen oder homogenen Inhalt. Nur einige weisen einen dichten zentralen Kern auf oder einen unregelmäßigen dichten zentralgelegenen Stab. Dieα-Zellen haben einheitlich runde und dichte, durch eine Membrane begrenzte Granula und sind spärlich verteilt, außer an der Peripherie der Inseln. Im frühen Diabetes mellitus sind dieβ-Zellen in großer Zahl vorhanden aber erscheinen entweder degranuliert oder in verschiedenen Phasen der Glykogenablagerung. In späteren Stadien der Krankheit, als Folge des allmählichen Verschwindens derβ-Zellen, bestehen die Inseln fast nur noch ausα-Zellen.
    Notes: Summary Islets of Langerhans of 15 Chinese hamsters (7 diabetic and 8 either related or unrelated controls of the same sex and age) have been examined by electron microscopy. Beta cells of control animals predominate and have abundant granules most of which are vesicles of varying sizes with a pale granular or homogeneous content. Only a few have a dense central core or irregular dense central bar. Alpha cells have uniformly round, dense, membrane-limited granules and are sparse except at the periphery of the islet. Early in diabetes mellitus beta cells are abundant but either agranular or in various stages of glycogen storage. Late in the disease the islets are reduced to almost all alpha cells, the beta cells having gradually disappeared.
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  • 6
    ISSN: 1432-0428
    Keywords: Spontaneous Diabetes ; Chinese hamster ; Cricetulus griseus ; Islet volume ; Beta cell volume ; Pancreas ; Beta cells ; Prediabetes ; Preclinical diabetes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons étudié 3 groupes de hamsters chinois de la colonie des laboratoires Upjohn, soit (1) des animaux diabétiques ayant présenté des symptômes pendant 18 mois; (2) des animaux non-diabétiques des mêmes nichées; et (3) des animaux non-diabétiques et non-apparentés mais concordant par l'âge et le sexe. Le diabète spontané de ces animaux est caractérisé par une hyperglycémie, une glucosurie, une diminution du volume des îlots de Langerhans, une diminution du volume total des cellulesβ, une dégranulation des cellulesβ et l'infiltration en glycogène des îlots de Langerhans. Des anomalies de même type, mais moins marquées ont été observées chez les frères et soeurs des animaux diabétiques. A notre connaissance, c'est là la première description de la diminution de la masse des cellulesβ et de leur dégranulation avant l'apparition clinique d'un diabète spontané chez l'homme ou l'animal. Il en ressortirait que cette altération des cellulesβ pourrait bien être un mécanisme étiologique primaire de la pathogénèse du diabète spontané du hamster chinois.
    Abstract: Zusammenfassung Drei Gruppen von chinesischen Hamstern aus der Upjohn-Zucht wurden untersucht. Dazu gehörten: diabetische Tiere, die seit 18 Monaten Symptome aufwiesen, nichtdiabetische Tiere aus gleichem Wurf und nichtverwandte nichtdiabetische Tiere, die in Alter und Geschlecht den anderen entsprachen. Der Spontandiabetes zeichnet sich aus durch Hyperglykämie, Glykosurie, Abnahme des Inselvolumens, Verminderung derβ-Zellmasse, Degranulierung derβ-Zellen und Glykogeninfiltration der Inseln. In den nichtdiabetischen Geschwistertieren wurden ähnliche aber weniger markante Veränderungen festgestellt. Unseres Wissens ist dies der erste Bericht einer Verringerung derβ-Zellmasse mit Degranulierung noch ehe sich ein Spontandiabetes bei Mensch oder Tier manifestiert. Dies deutet darauf daß diese Veränderungen derβ-Zellen einen primären etiologischen Faktor bei der Entstehung des Spontandiabetes beim chinesischen Hamster darstellen könnten.
    Notes: Summary Three groups of Chinese hamsters bred at the Upjohn Laboratory were studied: these included diabetic animals in which symptoms were present for 18 months, non-diabetic siblings and non-related, non-diabetic animals of the corresponding age and sex. The spontaneous diabetes is characterized by hyperglycemia, glycosuria, decreased islet volume, decreased beta cell mass, beta cell degranulation and glycogen infiltration in the islets. In the non-diabetic siblings, similar but less marked changes were noted. To our knowledge this is the first reported observation of decreased beta cell mass and beta cell degranulation occurring prior to clinical onset of spontaneous diabetes in man or animal. It suggests that the observed alteration of beta cells is a primary etiologic mechanism in the production of spontaneous diabetes in the Chinese hamster.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 65-73 
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese hamster ; Cricetulus griseus ; Retina anomalies ; Testicular function ; Free fatty acids ; Glycoproteins ; Mucopolysaccharides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Plusieurs chercheurs ont utilisé les hamsters chinois de notre colonie pour leurs observations expérimentales et nous rapportons ici les résultats de plusieurs études. — Le groupe du Dr. H.R.Hautsler, initiateur de la colonie à Toronto, a étudié les altérations de la rétine chez les animaux présentant un diabète spontané ou un diabète de type métahypophysaire résultant de l'injection d'hormone de croissance et de cortisone. Des anévrismes artériolaires et capillaires sont observés chez quelque 30% des animaux avec diabète métahypophysaire, mais sporadiquement seulement chez les hamsters avec diabète spontané. — Le groupe du Dr. K.Schöffling a étudié les biopsies du tissu testiculaire. Proportionnellement à la gravité du diabète, on trouve chez les hamsters présentant un diabète spontané une inhibition de la spermatogénèse, avec réduction de lépaisseur de l'epithélium germmal et élargissement de la lumière des tubules séminifères. Les cellules de Leydig sont également réduites en nombre. L'apparence histologique ressemble à celle du tissu testiculaire de diabétiques humains. — Le groupe du Dr. J.Campbell a mesuré les taux d'acides gras libres (AGL) du sérum de hamsters chinois non-diabétiques. Ceux-ci dépassant de 4 à 9 fois (3 à 5 mEq/l) les taux observés chez le chien, le rat ou l'homme, des taux semblables ayant pourtant été mesurés chez le hamster doré. Le tissu adipeux épididymaire de hamsters chinois ne diffère pas de celui du rat par son contenu en lipides, mais il libère davantage de AGL dans le milieu d'incubation. Les hamsters chinois non-glucosuriques sont sensibles à l'action diabétogène de la cortisone, mais non pas à celle de l'hormone de croissance de mouton. La cortisone s'est montrée très active quant à son action hyperglycémique, accompagnée d'une élévation des taux d'insuline sérique et des taux d'AGL. — Dans notre propre laboratoire, nous avons mesuré les concentrations en glycoprotéines du plasma et le contenu en mucopolysaccharides de la peau de hamsters non-diabétiques, avec glycosurie intermittente, ou franchement diabétiques. Nous n'avons pas observé, de différences entre ces trois groupes d'animaux quant au profil immuno-électrophorétique, ou la concentration en composantes hydrocarbonées des protéines plasmatiques. La substance basale de la peau de hamster diabétique contient davantage de mucopolysaccharides que celle des animaux non-diabétiques du même âge. C'est ainsi que le contenu en acides uroniques de la peau d'un groupe de hamsters, avec un sucre sanguin à jeun de 60 mg% en moyenne, était de 579 μg par g de tissu sec, alors qu'il était de de 882μg pour un groupe d'animaux avec un sucre sanguin à jeun de 107 mg% en moyenne.
    Abstract: Zusammenfassung Mehrere Forscher haben mit Tieren aus unserer Kolonie gearbeitet, und dieser Bericht betrifft eine Reihe von verschiedenen Resultaten. — Dr. H.R.Hausler und Mitarbeiter haben die Kolonie in Toronto begonnen und sich hauptsächlich mit Veränderungen in der Retina von spontandiabetischen Tieren befaßt. Sie haben ebenfalls Beobachtungen gemacht bei Tieren mit Diabetes von metahypophysärem Typ, also nach Injektion von Somatotropin und Cortison. Aneurysmata der Arteriolen und Kapillaren wurden in etwa 30% der Tiere mit metahypophysärem Diabetes beobachtet, nur vereinzelt aber bei spontandiabetischen Hamstern. — Dr. K.Schöffling und Mitarbeiter haben die Veränderungen in Hodenbiopsien geprüft. In direktem Zusammenhang mit der Schwere des Diabetes findet man bei spontandiabetischen Hamstern verschieden ausgeprägte Hinweise auf inhibierte Spermatogenese, mit Verminderung der Zellzahl des germinalen Epitheliums und Erweiterung der Lumina der Tubuli seminiferi. Auch die Zahl der Leydig-Zellen ist vermindert, und das histologische Bild ist allgemein demjenigen beim Diabetiker ähnlich. — Dr. J.Campbell und Mitarbeiter haben bei nicht-diabetischen chinesischen Hamstern freie Fettsäuren (FFS) gemessen und haben beobachtet, daß deren Konzentration im Serum 4 bis 9 mal höher liegt (3 bis 5 mVa/l) als beim Hund, bei der Ratte und beim Menschen. Ähnlich erhöhte Werte findet man aber auch beim Goldhamster. Epididymales Fettgewebe von Ratten und chinesischen Hamstern enthielt etwa gleich viel Fett, aber das Fettgewebe chinesischer Hamster mobilisiertein vitro mehr FFS. Bei nichtdiabetischen Hamstern war Cortison diabetogen, nicht aber Somatotropin vom Schaf. Die Verabreichung von Cortison führte zu erhöhten Zuckerwerten, zu erhöhtem Seruminsulin und zu sehr hohen FFS-Konzentrationen. — In unserem eigenen Laboratorium haben wir den Gehalt an Glucoproteinen im Plasma und an Mucopolysacchariden in der Haut bestimmt, und zwar in nicht-diabetischen, in nur zeitweise glucosurischen, und in klinisch deutlich diabetischen Hamstern. Zwischen diesen drei Gruppen von Tieren ließen sich keine Unterschiede bezüglich auf immunoelektrophoretische Verteilung oder auf Zuckergehalt einzelner Komponenten der Plasmabestandteile nachweisen. Die Haut diabetischer Hamster enthielt aber mehr Mucopolysaccharide als diejenige nicht-diabetischer Hamster gleichen Alters. Hamster, deren Nüchternblutzuckerwerte bei 60mg% lagen, wiesen einen Uronsäuregehalt von 579 μg per g Trockengewebe auf, während der entsprechende Wert bei Tieren mit durchschnittlich 107 mg% Blutzuckernüchternwert 822μg war.
    Notes: Summary Several investigators have used Chinese hamsters from our colony for experimental work, and results of various studies are reported. — The group of Dr. H.R.Hausler, who initiated the colony in Toronto, studied retinal changes in spontaneously diabetic animals and also in hamsters with the metahypophyseal type of diabetes, following serial injections of growth hormone and cortisone. Arteriolar and capillary aneurysms were found in about 30% of the animals with metahypophyseal diabetes, but only sporadically in spontaneously diabetic hamsters. — The group of Dr. K.Schöffling studied alterations of testicular tissue in biopsy material. Corresponding to the severity of the disease, spontaneously diabetic hamsters showed various degrees of inhibited spermatogenesis, resulting in a reduction of the thickness of the germinal epithelium and widening of the lumina of the seminiferous tubules. There was also a reduction in the number of Leydig cells. The overall histological picture resembled that of the testes of the diabetic human patient. — The group of Dr. J.Campbell measured concentrations of serum free fatty acids (FFA) in nondiabetic Chinese hamsters and found the levels 4 to 9 times higher (3 to 5mEq/l) than in dogs, rats and man, but similar to FFA levels of Syrian hamsters.Epididymal fat pads of rats and Chinese hamsters showed similar lipid contents, but the latter released more FFA into the incubation medium. Nonglycosuric hamsters were susceptible to the diabetogenic effect of cortisone, but not to ovine growth hormone. Cortisone was most effective in producing a high blood sugar and elevated serum insulin and FFA concentrations. — In our own laboratory, the concentration of glycoproteins in plasma and the mucopolysaccharide content of the skin were determined in nondiabetic, occasionally glycosuric and frankly diabetic hamsters. There was no difference amongst the three groups of animals with regard to either the immunoelectrophoretic pattern or the concentration of individual carbohydrate components of plasma proteins. Skins of diabetic hamsters contained more mucopolysaccharide in their ground substance than skins of nondiabetic animals of comparable age. Hamsters with a mean fasting blood sugar value of 60 mg% showed a uronic acid content of 579μg per g of dry tissue, whereas animals with a mean fasting blood sugar of 107 mg% had 822μg.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 124-129 
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese hamster ; Cricetulus griseus ; Inheritance of diabetes ; Genetics of diabetes ; Polygenic system of inheritance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé 1. Nous avons analysé les pedigrees et les estimations de glucosurie (Tes-Tape) de plus de 6000 hamsters chinois de la colonie du Best Institute à Toronto et de celle de la maison Upjohn à Kalamazoo. A Toronto, la distribution des estimations au Tes-Tape était de 23%+, de 6%++, 3%+++, et de 5%++++. L'incidence du diabète a augmenté durant les 11 premières générations de consanguinité, elle a légèrement diminué par la suite L'incidence du diabète est plus grande dans la colonie Upjohn, les nichées étant plus petites et le nombre des morts avant sevrage plus grand. Lorsqu'un ou deux parents sont diabétiques, 40% des rejetons ne survivent pas; 14% seulement, lorsque les deux parents ne sont pas diabétiques. Par rapport à tout autre type d'accouplement, les parents non-diabétiques donnent naissance à un nombre légèrement moindre de diabétiques et nettement moindre d'animaux à faible glucosurie. — 2. Nous concluons de ces données que le diabète du hamster chinois est héréditaire mais qu'aucun système simple de transmission n'est à même de cadrer avec elles. C'est pourquoi nous proposons un système composé d'un minimum de 4 gènes dont la coïncidence de deux en homozygocité récessive mène à un diabète patent. Le nombre des possibilités données par un système récessif quadruple associé à la moindre capacité de survie des diabétiques permet de prévoir que le croisement diabétique x diabétique ne produira des diabétiques qu'une fois sur 6. — 3. Les polygènes agissent sur divers systèmes physiologiques et non pas sur un gène diabétique »caché«. Le syndrome diabétique est le résultat de l'action de ces gènes sur la production d'enzymes, la prolifération des cellules, la perméabilité des membranes et le métabolisme de différents tissus. Aussi nous ne devrions pas nous attendre à ce que tous les hamsters diabétiques se ressemblent et soient caractérisés, par exemple, par une rétinopathie ou une hydronéphrose, mais une plus grande fréquence de manifestations semblables est probable pour chaque lignée.
    Abstract: Zusammenfassung 1. Von über 6000 Hamstern der Kolonie des Best Instituts in Toronto und der Upjohn-Kolonie in Kalamazoo wurden die Stammbäume und Tes-Tape-Ergebnisse geprüft. Dabei ergab sich, daß in der Best'schen Kolonie mit Tes-Tape 23%+, 6%++, 3%+++ und 5%++++ reagierten. Während der ersten 11 Generationen Inzucht stieg das Vorkommen von Diabetes an und fiel danach leicht ab. In der Upjohn-Kolonie, wo das Auftreten von Diabetes häufiger war, waren die Würfe kleiner und die Sterbeziffer unter den noch nicht entwöhnten Jungen höher. Wenn einer oder beide Elternteile diabetisch waren, starben 40% der Jungen im Gegenteil zu 14% bei anderen Paaren. Normale Eltern hatten im allgemeinen weniger diabetische Junge, und die Zahl der Tiere, die nur Spuren Glucose im Urin aufwiesen, war wesentlich geringer als bei anderen Paarungstypen. — 2. Daraus wurde geschlossen, daß Diabetes beim chinesischen Hamster zwar erblich ist, daß die Ergebnisse aber nicht in ein einfaches Vererbungsschema einzugliedern sind. Es wird ein polygenetisches System vorgeschlagen, mit mindestens 4 Genen, von denen jeweils die Homozygotie von zwei Diabetes hervorruft. Wegen der Möglichkeiten, die sich aus den 4 rezessiven Genen ergeben, sowie wegen der geringeren Überlebenskraft der zu Diabetes Prädisponierten, erzeugt eine Paarung von 2 Diabetikern nur in einem Fall von sechs ebenfalls einen Diabetes. — 3. Die Polygene wirken auf verschiedene physiologische Systeme und nicht auf ein „ruhendes“ diabetisches Gen. Das diabetische Syndrom ist das Ergebnis der Wirkung dieser Gene auf Enzymproduktion. Zellwachstum, Membrandurchlässigkeit und allgemeinen Stoffwechsel in den verschiedenen Geweben. Daher ist nicht zu erwarten, daß alle diabetische Hamster Retinopathie oder Hydronephrose aufweisen, jedoch ist zu erwarten, daß die gleichen Erscheinungsmerkmale innerhalb eines Zuchtstammes gehäuft auftreten.
    Notes: Summary 1. The pedigrees and Tes-tape scores of over 6000 hamsters in the Best colony in Toronto and the Upjohn Colony in Kalamazoo were examined. It was found that the distribution of Tes-tape scores in the Best colony was 23%+, 6%++, 3%+++, and 5%++++. The incidence of diabetes rose for the first eleven generations of inbreeding then fell off slightly. In the Upjohn colony, which had a higher incidence of diabetes, the litter sizes were smaller and the pre-weaning deaths greater. When one or both of the parents were diabetic 40% of the young died as opposed to 14% for other matings. Non-diabetic parents produced slightly less diabetics and significantly less trace animals than did any other type of mating. — 2. It was concluded that diabetes is inherited but that no simple system of inheritance will fit the data. A polygenic system is postulated with a minimum of four genes any two of which when homozygus recessive will cause diabetes. Because of the variety of the quadruple recessive and the lower viability of diabetics, the mating diabetic x diabetic will breed true one mating in six. — 3. The polygenes act on various physiological systems and not on a “dormant” diabetic gene. The diabetic syndrome is the result of the action of these genes on enzyme production, cell proliferation, membrane permeability, and general metabolism, in various parts of the body. Thus one would not expect all diabetic hamsters to exhibit retinopathy or hydronephrosis, but one would expect predominantly the same manifestations within the same subline.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 266-286 
    ISSN: 1432-0428
    Keywords: Spontaneous Diabetes ; Chinese hamster ; Cricetulus griseus ; Kidney ; Renal glomerulopathy ; Capillaries ; Basement membrane ; Ultrastructure ; Mesangium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons étudié aux microscopes optique et électronique les glomérules rénaux de 11 hamsters chinois non-diabétiques, de 4 hamsters non-diabétiques mais provenant de nichées comportant des animaux diabétiques, et de 6 animaux ayant souffert d'un diabète de durée et de sévérité variables. Le vieillissement en soi est associé à une augmentation du mésangium et à une dilatation des capillaires avec léger épaississement de la membrane basale. Chez les diabétiques sévères de type juvénile, nous avons observé des altérations profondes des cellules mésangiales, avec la formation de vésicules, de corps multivésiculaires, de vacuoles et une apparence lavée du cytoplasme avec désorganisation mitochondriale. Ce n'est qu'aux stades les plus avancés qu'on observe une augmentation de la matrice mésangiale. Aux premiers stades, les membranes basales sont minces, particulièrement pour les capillaires dilatés. A des stades plus avancés, on trouve des régions épaisses et des régions minces de la membrane basale; certainement pas d'épaississement généralisé. Bien que des altérations semblables eussent été observées avec le vieillissement simple, les altérations des cellules mésangiales, la coalescence, la dilatation cystique et la fusion des anses capillaires des glomérules sont caractéristiques d'une glomérulopathie diabétique chez les animaux jeunes. Les altérations sont beaucoup plus marquées à des stades plus avancés de l'état diabétique. La diminution du nombre des anses capillaires est probablement le résultat de la coalescence des capillaires. Les cellules épithéliales sont bien préservées dans tous les glomérules et il n'y a pas de lésions nodulaires. Nous n'avons pas observé de lésions glomérulaires semblables chez les frères et soeurs des animaux diabétiques ne souffrant pas eux-mêmes d'un diabète patent. Il semblerait y avoir une analogie entre la dilatation et la coalescence des capillaires du glomérule en présence d'altérations des cellules mésangiales et la dilatation des capillaires rétiniens associée à la dégénérescence des cellules murales, ou péricytes, chez l'homme.
    Abstract: Zusammenfassung Wir haben im Licht- und im Elektronen-Mikroskop die renalen Glomeruli von 11 Kontrolltieren, von 4 nicht-diabetischen Tieren aus gleichem Wurf wie diabetische Hamster, und von 6 Tieren mit Spontan-Diabetes verschiedenen Alters, sowie mit unterschiedlicher Dauer und Schwere des Krankheitsbildes, untersucht. Zunehmendes Alter führte zur Zunahme der mesangialen Matrix mit einiger Erweiterung der Kapillaren und Verdickung der Basalmembran. Bei früh einsetzendem schweren Diabetes wurden schwere Veränderungen der Mesangialzellen beobachtet, bestehend aus Vermehrung der vesikulären Bläschen, Entstehung von multi-vesikulären Strukturen, Vacuolen, und einem verwaschenen Aussehen des Zytoplasmas, sowie mitochondrialer Desorganisation. Bei vorgerücktem Krankheitsbild bestand eine deutliche Zunahme der mesangialen Matrix. Anfänglich war die Basalmembran dünn, besonders in den erweiterten Kapillaren. Später, wies die Basalmembran sowohl verdickte wie verdünnte Stellen auf. Obwohl ähnliche Veränderungen auch mit zunehmendem Alter zu sehen waren, ließ die Beobachtung von Veränderungen der mesangialen Zellen, von zystischer Erweiterung und Verschmelzen von Kapillarschlingen beijungen Hamstern sicher auf diabetische Glomerulopathie schließen. Diese Veränderungen waren denn auch verhältnismäßig noch deutlicher und besonders charakteristisch in späteren Stadien der Krankheit. Die Fusion von Kapillaren erklärt vielleicht die Abnahme der Zahl der Kapillarschlingen. Die Ausläufer der Epithelialzellen blieben in allen Glomeruli wohl erhalten und es waren keine noduläre Läsionen zu sehen. In den von uns beobachteten Tieren waren solche Veränderungen der Glomeruli bei nicht-diabetischen Tieren nicht zu sehen. Es wird darauf hingewiesen, daß zwischen der Erweiterung und der Fusion von Kapillarschlingen, im Zusammenhang mit Veränderung der mesangialen Zellen, und der Erweiterung von Kapillaren der Netzhaut, im Zusammenhang mit Degeneration deren Perizyten beim Menschen, eine Analogie besteht.
    Notes: Summary Light and electron microscopic studies were made of the renal glomeruli of 11 control Chinese hamsters, 4 siblings of diabetic hamsters, and 6 with spontaneous diabetes of varying age of onset, duration, and severity. Aging alone was associated with an increase in mesangial matrix and some degree of capillary dilatation and thickening of the basement membrane. In severe diabetes of early-onset, there was a marked change in mesangial cells, consisting of an increase in vesicles, multivesicular bodies, vacuoles, ghost-like appearance of the cytoplasm, and mitochondrial disorganization. Only in the more advanced stages was there an increase in the mesangial matrix. Initially, the basement membrane was thin, particularly in dilated capillaries. Measurements of the basement membrane in the later stages indicated that there were both thick and thin areas; increased thickness alone was not characteristic. Although similar findings developed progressively with age, mesangial cell alterations, coalescence and cystic dilatation and fusion of capillary loops in the glomeruli of young hamsters were characteristic findings of diabetic glomerulopathy. These findings were characteristic and disproportionately marked in any later stage of the disease. Coalescence of capillaries may have explained the decrease in the number of loops. The foot processes of the epithelial cells were well-preserved in all glomeruli and nodular lesions were not seen. There was no evidence in this series that litter-mates of diabetic animals developed such glomerular lesions in the absence of overt diabetes. An analogy was suggested between the dilatation and coalescence of glomerular capillaries associated with mesangial cell changes and the dilatation of retinal capillaries associated with degeneration of the supporting mural cells in man.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 1-4 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigations have been made on the optical rotatory dispersion properties of E. coli ribosomes and their constituent RNA and proteins. The results indicate that (1) no conformational changes are involved in the formation of a 70S particle from the 50S and 308 subunits, (2) the E. coli ribosomal proteins are similar to most globular proteins with little α-helix content, and (3) the conformation of RNA and proteins inside the ribosome is very similar to that in the free state.
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  • 11
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The iodine which is added to an aqueous amylose solution is bound only partly by the amylose while forming the blue complex and partly remains free. The equilibrium normality of the free and the bound iodine at half-saturation of amylose by iodine is designated as [If]v and [Ib]w, respectively. The stability of the poly iodine chain formed within the axis of amylose helices depends on its length, i.e., indirectly on the DP of the amylose helices: the greater this stability, the lower the [If]v value. The amylose molecule consists of helical segments. Such a molecule may behave as a random coil. The average length of the helical segments in freshly prepared amylose-iodine complexes depends on temperature, pH, iodide concentration, the presence of other complex-forming agents, and the DP of the amylose. This latter factor is investigated in the present paper. By the aid of an automatically recording photometrictitrating device the coherent values of [Ib] and [If] were determined. Plotting these values against DPn for mechanochemically degraded as well as for periodateo-xidized amyloses resulted in curves consisting of two linear sections. The break of the curves occurred between DPn 110 and 130. It was concluded that below DPn = 100 the DP of helical segments (= sDPn) is identical to the DPn of the total molecule, i.e., the molecule consists of only a single, relatively stiff helix. Above this limit the molecule contains several helical segments. The DP of these helical segments can be calculated as follows: sDPn = 141.1 - 10.2 × 105[If]v. This equation is considered to be valid for 0.5-0.6 mg. amylose in 100 ml. 0.1N HCl at 20°C., λ = 650 mμ, euuvet diameter 3.4 cm., the feed rate of the iodate-iodide titrating solution (in acid medium resulting in a 5 × 10-3N I2 solution with a molar iodide to iodine ratio of 1.5) is 0.4ml./min. Amylose molecules of, e.g., DPn = 1380 consist of an average of 11.4 segments having a DP of about 120 and consisting of an average of 15-18 helical turns.
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 61-68 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemical possibilities for investigation of nucleic acids with high molecular weight are restricted to the determination of the adsorption behavior. According to our experience the alternating current polarography (Breyer-polarography) is mainly appropriate for the characterization of changes in the secondary structure of DNA. The Breyer-polarogram shows the alternating current of the dropping electrode in dependence on their potential which varied from 0-2 v. negative against the normal calomel electrode (NCE). By addition of native DNA to the supporting electrolyte (buffer solution) the current drops down in the range of adsorption between 0 and 1 v. At 1.16 v. against NCE the desorption takes place together with the formation of a rounded desorption peak. The investigation was carried out in phosphate buffer solution 0.1m with 0.075m NaCl or in a phosphate buffer 0.18m with 0.03m NaCl. In the pH range above pH 8 NaOH was added to realize the higher pH values. A calf thymus DNA sample having a mean molecular weight of about 18 million was used. The concentration of DNA was 5 × 10-3-1 × 10-1 wt.-%. The polarographic measurements were performed with an a.c./d.c.-polarograph “GWP 564” from Akademiewerkstätten für Forschungsbedarf der Deutschen Akademie der Wissenschaften zu Berlin (DAW). The denaturation of the double helix causes a sharp desorption peak at negative potentials of the alternating current polarogram. This new criterion for the helix-coil transition is due to formation of unpaired bases. These nearly free bases undergo a specific adsorption and the desorption takes place within a narrow potential range. Nevertheless, at present time an electron transfer to particular bases cannot be excluded at special conditions. The increase of the sharp peak permits to estimate: (a) the melting curve of the double helix in agreement with spectroscopic measurements; (b) the photolysis of the double helix; (c) the strand separation in acid and alkaline solution. In the alkaline range the sharp peak increases and reaches its maximum at pH 〉 12. In the acid range, however, no sharp peak is observed and the rounded desorption peak decreases. Therefore, the best way of following the conformation changes is to measure the current difference between the curves of the solutions with and without DNA at electrocapillary-zero-potential. On the classical d.c.-polarogram one can measure small current steps only, which may be caused mainly by capacity changes. Moreover, the scission of the molecule by ultrasonic action can be followed. In this case the rounded peak of DNA increases but the sharp peak does not appear. Similar alternating current polarograms are obtained with poly-A in the native state, because helical and unordered regions coexist in the same molecule. The very rapid indication of these structure changes allows one to carry out kinetic measurements at a fixed potential with this method.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 135-148 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The theory of Kirkwood for the translational frictional coefficients of structures composed of subunits has been generalized in two ways in order to consider aggregates of nonidentical subunits. One of these generalizations fails when the sizes of subunits are too disparate; the other, derived from a surface shell distribution of frictional elements, is effective over the whole range of relative sizes. It is shown that, in the limit of a continuous surface distribution, a shell model reproduces Stoke's law for a sphere. Comparison is made between the frictional coefficients of spheres, ellipsoids, and rods modeled by finite numbers of subunits and by continuous shells of frictional elements, and those calculated from other theories. Agreement is generally good, though the shell model for prolate ellipsoids of revolution deviates by a few per cent from the Perrin value.
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 589-613 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of matrix rank analysis has been applied to a large body of experimental data to determine and identify the minimum number of independent spectral components that, were contained within it. The optical rotatory dispersion of TMV RNA was measured in the wavelength region 230-350 mμ, for a wide range of temperatures and ionic strengths. Over the whole range of conditions considered, the observed optical rotatory dispersion spectra were found to be a superposition of two basic spectra only. Evidence is put forward relating these spectra to the single-strand and double-strand helical forms of the molecule. A model is proposed to explain the observed spectral changes in terms of an equilibrium between these two conformations, which leads to a direct calculation of the percentage composition of the double strand at any of the conditions considered. This equilibrium, while simple in general description, appears multi-state and complex in detail. This method of analysis is both powerful and of wide applicability, since it is independent of the source of the data.
    Additional Material: 15 Ill.
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  • 15
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An infinite series solution to the Mason-Weaver equation is presented for the case in which a synthetic boundary is formed originally between solution and solvent. Digital computations based on this series, and confirmed independently, have been made for a range of parameters. For given conditions, the maximum rate of change of concentration at the meniscus and the time at which it occurs can be easily estimated by means of the curves presented. In equilibrium experiments which commence with formation of a sharp boundary, this enables the fringes to be identified with certainty.
    Additional Material: 6 Ill.
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  • 16
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The course of the reversible helix formation of poly(γ-benzyl L-glutamate) (PBG) dissolved in a mixture of dichloroacetic acid (DCA) and 1,2-dichloroethane (EDC) was followed by measuring the heat capacity and the optical rotation of the system through the transition region. The results of these measurements indicate that the transition enthalpy ΔH the transition temperature Tc, and the Zimm-Bragg parameter σ depend considerably on the PBG concentration as well as on the composition of the solvent. For the standard state of infinite dilution, however, a linear extrapolation of the measured ΔH if values results in a standard value ΔH° = 950 cal./mole, independent of the solvent composition. The results of the calorimetric measurements are discussed in relationship to changes in optical rotation. Some peculiarities in the measured thermodynamic and optical properties in solutions with relatively high content of dichloroacetic acid are reported.
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  • 17
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    Biopolymers 5 (1967), S. 673-679 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Helical conformations of infinite polymer chains may be described by the helical parameters, d and θ (the translation along the helix axis and the angle of rotation about the axis per repeat unit), pi (the distance of the ith atom from the axis), dij, and dij (the translation along the axis and the angle of rotation, respectively, on passing from the ith atom to the jth). A general method has been worked out for calculating all those helical parameters from the bond lengths, bond angles, and internal-rotation angles. The positions of the main chain and side chain atoms with respect to the axis may also be calculated. All the equations are applicable to any helical polymer chain and are readily programmed for electronic computers. A method is also presented for calculating the partial derivatives of helical parameters with respect to molecular parameters.
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  • 18
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    Biopolymers 5 (1967), S. 685-689 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A dilatometric technique is employed to measure the volume changes occurring on denaturation of collagen solutions and tendons. Partial specific volumes of tropocollagen are calculated to be 0.686 ml./g. in water and 0.689 ml/g in 0.1M citrate buffer. From data on non-aqueous solutions, it is estimated that most of the volume change arises from changes in polymer configuration rather than from changes in solvation.
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  • 19
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    Biopolymers 5 (1967), S. 697-713 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have generated solutions to the Lamm equation to examine the effects of concentration dependence on velocity experiments. Two forms of c dependence are considered: s/s0 = 1 - kc and s/s0 = (1 + kc)-1. Features of these solutions are discussed. The magnitude of the errors resulting from the usual procedure of measuring the rate of movement of schlieren maxima or of the position at which the concentration is one half the plateau value have been examined. These errors are usually negligible after sufficient centrifugation time. The errors in using the half-plateau concentration are less than those using the movement of the peak. We have also examined a technique due to Fujita for determining D from boundary spreading when s/s0 = (1+kc)-1. This method is satisfactory when s/s0 is actually of this form, or under certain limitations when s/s0 = (1 + kc)-1. Creeth has shown that under certain conditions the concentration gradient, curve remains virtually unchanged in shape after separating from the meniscus. When this occurs it is possible to estimate s/D from the data. The condition for such a steady state is that kc0 be sufficiently large. Numerical confirmation of this method is presented in the final section.
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  • 20
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    Biopolymers 5 (1967), S. 723-726 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preliminary experiments have been carried out which measure the variation in the intensity of the light scattered by DNA solutions under the influence of an electric field. Data have been collected on the length of DNA molecules, their electric polarizability, and their dispersion behavior.
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  • 21
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Information concerning the structures of rA-rU, rA-rU2 rI-rC, rA-rI2, and acid rA helices in solutions is reported. Through the use of diquaternary ammonium salts of the general structure, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}_1 {\rm R}_2 {\rm R}_3 \mathop {\rm N}\limits^ + ({\rm CH}_2 )n\mathop {\rm N}\limits^ + {\rm R}_1 {\rm R}_2 {\rm R}_3 \cdot 2{\rm Br}^ - $\end{document} (I), it is shown that (1) the distances between adjacent negatively charged oxygen atoms on the helix increases in the following order rA-rI2 〈 rI-rC 〈 rA-rU ≤ rA-rU2; (2) the density of the helices increases in the order. rA-rI2 〈 rA-rU 〈 rA-rU2 〈 rI-rC; (3) there is a large hydrophobia site in rA-rI2 and possibly also in rA-rU, rA-rU2, and rI-rC helices; (4) the results of the interactions between the salts of type I and the helices may be formulated in semi-quantitative terms by the use of two parameters, α, and β which are shown to be related to the charge separation and the density of the helices, respectively; (5) the studies in solutions compare favorably with the x-ray studies on the fibers; and (6) the acid rA helix differs significantly from the other helices by the fact that the electrostatic interstrand interactions between the negatively charged oxygen atom of a phosphate group and the positively charged 10-amino group of adenine contribute significantly to the stabilization of the helix, and thus it is found that the presence of the salts, I, leads to a significant destabilization of the acid rA helix.
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  • 22
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The half molecules of 186 DNA have been isolated by the Hg(II)-Cs2SO4 density gradient centrifugal ion technique. The buoyant densities of the two halves in CsCI at 25°C. are 1.713 and 1.709 g./cm.3, corresponding to GC contents of 54% and 50%, respectively. Similarly, 5-bromouracil labeled λ DNA halves were separated. The isolation of the four DNA halves made it possible to test for homology in base sequences between the cohesive ends of λ and those of 186. There was no indication of any significant homology in base sequences between the cohesive ends of the two DNA's, as indicated by the absence of a band with intermediate buoyant density in CsCI when either half of 186 DNA was annealed with either half of 5-bromouracil labeled λ DNA and then centrifuged. The lack of cohesion between the two DNA's made it possible to demonstrate unequivocally the formation of interlocked rings (catenanes) between the two DNA's. The existence of a dimeric catenane is evidenced by the formation of a species of intermediate buoyant density when 5-bromouracil labeled λ DNA is cyclized in the presence of cyclic 186 DNA of a relatively high concentration. The molecular weight of one DNA relative to the other can be calculated from the position of the dimeric catenane in a density gradient by using the method of Baldwin. The result was in complete agreement with our previous measurements from the sedimentation coefficients and by electron microscopy. The probability of dimeric catenane formation when one DNA is cyclized in the presence of another DNA is discussed. The experimental results agree with the theoretical expectation.
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  • 23
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    Biopolymers 5 (1967) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 24
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    Biopolymers 5 (1967), S. 815-820 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sterically allowed forms of the poly-N-methyl-L-alanine chain were found by calculation of conformational energies as a function of the rotation angles of its chain bonds. The lowest energy form seems to be a right-handed, approximately threefold helix.
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  • 25
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    Biopolymers 5 (1967), S. 837-845 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oriented amylose fibers in the V form were prepared and subjected to x-ray analysis. Unit cells and the probable space group of P212121 were determined for the V anhydrous and V hydrate forms of amylose; the analysis confirms previous predictions of these structures based on x-ray powder patterns. Chain folding in V amyloses is discussed in view of crystallographic evidence and folding experiments conducted with space-filling models. Reported also is evidence for amylose helices having diameters intermediate between 13.0 and 13.7 A.
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  • 26
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energies of the poly-N-methyl-L-alanine chain have been calculated as a function of the rotational angles of its skeletal bonds, taking into account torsional potentials, van der Waals repulsions, and London attractions. Four pronounced minima in the energy were found; the relative magnitudes of the energies at these minima suggest that the preferred conformation of this chain is either a right-handed, approximately threefold helix, or a slightly distorted, left-handed α-helix. Inclusion of an estimate of the dipolar contribution to the total conformational energy does not significantly affect this conclusion.
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  • 27
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equilibrium normality [If] of free iodine in amylose-iodine complex formation is a function of the length of the polyiodine chains. This length depends on the DP of helical segments of amylose (sDPn). Values of [If] and of the concentration of the bound iodine [Ib] were determined by the continuous photometric titration with automatic recording. Plots of [Ib] versus [If] give an integral distribution curve. Since the relation between [If] and sDPn is known, the graphic differentiation of the [Ib] versus [lf] curve furnishes the differential distribution curve, representing the mass distribution of the helical segments according to their DP. The peak of this curve is characteristic of the percentage and DP of those helical segments, which occur in the largest amount. On the basis of the differential distribution curve the polymolecularity of the investigated sample may be judged. The titration of amylose samples degraded by various methods gives different distribution curves. Titrating mixtures of samples with widely differing average DP values results in differential curves having more than one maximum.
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  • 28
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    Biopolymers 5 (1967), S. 79-94 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electronic absorption and circular dichroism spectra of the DNA-acridine orange complex have been measured over a range of ionic strength, pH, and DNA phosphate to dye (P/D) ratios. Three circular dichroism bands associated with the long wavelength absorption band of acridine orange are induced on complex formation with DNA. Two of the dichroism bands, due mainly to dimeric dye molecules, are favored by low ionic strength, low pH (3.2), and a low P/D ratio (∼3), while the third, deriving primarily from monomeric dye, is optimum at high ionic strength, neutral pH, and a larger P/D ratio (9). The data suggest that monomeric acridine orange binds to DNA in the form of a left-handed helical array with four dye molecules per turn, while the bound dimer has a skewed sandwich conformation which is itself dissymmetric. The stereochemical relations between the bound monomer dye and the DNA are consistent with a modified intercalation model for the DNA-acridine complex.
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  • 29
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    Biopolymers 5 (1967), S. 69-77 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The degree of helicity θ of a series of homologous polypeptides as a function of solvent composition was investigated. The polypeptides studied were: poly-N5-(3-hydroxypropyl)-L-glutamine (PHPG) as well as the corresponding 2-hydroxyethyl and 4-hydoxybutyl derivatives (PHKG and PHBG, respectively). PHPG, which is nonhelical in formic acid, attains helicity on addition of relatively small amounts of formates, formamide, and urea to its solution in formic acid. This demonstrates that the high acidity of pure formic acid is largely responsible for its helix-breaking power-probably through protonation of the peptide bonds. In formic acid-water mixtures all three polymers show a maximum in degree of helicity at a mole fraction of about 0.3 formic acid. This is interpreted as being due to interaction between the two helix-breaking solvents, which results in the formation of an inactive molecular species. It is shown that solvent-induced transitions with helicity maxima are predicted by the Bixon-Lifson treatment when applied to this system.
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  • 30
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    Biopolymers 5 (1967), S. 879-886 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dielectric properties of human and horse hemoglobin were studied at frequencies ranging from 20 kc./sec. to 7 Mc./sec. The relative errors in the measurements were usually less than 10-3 even for mildly conducting solutions (10-3M KCl). The experimental setup allowed us variation and measurement of the degree of oxygenation of the protein and to determine its dielectric parameters. Our main conclusion is that it was not possible to find any variation of the dielectric increment for hemoglobin oxygenation levels of 25, 50, 75, and 100%, approximately. This result is at variance with some previous reports. We cannot give the reason for this discrepancy but discuss some possible explanations. The specific dielectric increment, Δεs/c, of human hemoglobin was shown to be significantly smaller than that of horse hemoglobin (0.28 against 0.32). This physical property is lowered with increasing ionic strength I: Δεs/c = 0.28 and 0.20 for I = 10-4 and 10-3, respectively (human protein).
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  • 31
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    Biopolymers 5 (1967), S. 773-783 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An expression is derived for the melting point of a polymer when in equilibrium with a solution in which binding of low molecular weight compounds to the polymer takes place. Allowance is made for the possibility that the crystalline polymer itself is a complex. The argument is a purely thermodynamic one and is based on a consideration of the change in free energy as a result of a change in binding. Allowance is made also for non-specific polymer-solvent interactions, in which the mixture of low molecular weight solvents is treated as a single solvent. Special attention is paid to “inverted” melting transitions, i.e., cases in which the melting point increases with increasing dilution of the polymer. It is shown that as a rule this is accompanied by a corresponding, inverted effect of the solvent composition on the melting point. It is further shown that-in the absence of binding, “normal” behavior at the critical point (i.e., phase separation is induced by lowering the temperature) is always accompanied by “normal” melting behavior (i.e., a decrease in melting point when the polymer is diluted). Also, “inverted” melting always implies that phase separation at the critical point is induced by heating, but the reverse is not necessarily true.
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  • 32
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    Biopolymers 5 (1967) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 33
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    Biopolymers 5 (1967), S. 27-35 
    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 temperature Tc of poly(γ-benzyl L-glutamate) in binary solvent mixtures of dichloroacetic acid and 1,4-dichlorobutane, 1-chlorooctane, or 1-chlorododecane have been measured. A treatment is presented with which the transition enthalpy can be calculated from the observed dependence of Tc on solvent composition. Results are compared with previously obtained calorimetric data. The underlying assumptions of the calculation are discussed.
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  • 34
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    Biopolymers 5 (1967), S. 37-59 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A marked molecular weight fractionation accompanies the demixing or phase separation resulting from the complex coacervation of mixtures of aqueous solutions of salt-free isoionic unfractionated gelatins with pI's of 5 and 9. Viscosity studies show that the fractionation is such that the concentrated phase tends to maintain constant, homogeneous composition. A second feature, seen in phase volume and concentration measurements, is a marked self-suppression of coacervation intensity with increasing mixing concentration. These data were interpreted in terms of a dilute-phase aggregate model which assumes nearly equal electrostatic free energies of mixing in dilute aggregate and concentrated random phase. The driving force for phase separation is the entropy increase upon formation of the random phase but demixing also depends upon the polymer-solvent interaction parameter χ, in the same fashion as in simple coacervation. The dilute-phase aggregate model indicates that the sharp molecular weight selection takes place in the aggregate formation step and explains the self-suppression. Phase equilibria studies utilizing fractionated, paucidisperse high molecular weight gelatins, emphasize the requirement for concentrated phase homogeneity and indicate that aggregates of different molecular weight may act as different components, so that χP1Q1,PkQk 〉 0, bringing about a separation of the system into three or more coexisting phases. The formation of several coexisting phases from a homologous polyelectrolyte system and the very marked requirement for phase homogeneity suggest that the phenomenon of complex coacervation is a very good model for some of the essential steps in the pre-biologic organization of polymeric polyions.
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  • 35
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Light scattering of multichain poly-α-amino acids was studied in dimethylformamide (DMF). The polymers consisted of a backbone of poly-L-lysine of degree of polymerization n with side chains of benzyl L-glutamate and benzyl L-aspartate of degree of polymerization, m, on each ε-amino group. The backbone length n is known and m is obtained by amino acid analysis. The results on a series of such materials confirm this structure and show that the molecules are dissolved in highly compacted conformations. It was found that DMF is a poor solvent for these polymers. In the case of the higher molecular weight polymers, the solutions initially were not molecularly disperse. The aggregates were resistant to dilution in the experimental range. Mild heat treatment, however, disaggregated the solutions irreversibly, and the light-scattering data indicated that a structural rearrangement of the molecules had occurred.
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  • 36
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    Biopolymers 5 (1967), S. 105-122 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The intrinsic viscosity, sedimentation and diffusion of a series of branched, multichain poly-α-amino acids having a poly(L-lysine) backbone and poly(γ-benzyl L-glutamate) and poly (β-benzyl L-aspartate) side chains was studied at room temperature in dimethylformamide. The molecules were found to be extremely compact structures in which the molecular backbone is either lying along the major axis in a slightly twisted configuration (the longer the side chain the smaller the twist) or is coiled up in the form of a disk with backbone and side chains coplanar. Heat treatment (to 70°C.) introduces only small changes in the hydrodynamic parameters showing that the heat-labile aggregates detected by light scattering are reversibly broken up during the hydrodynamic measurements. The above structural information concerns the initial metastable conformation of the molecules which is irreversibly destroyed by heat treatment.
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  • 37
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    Biopolymers 5 (1967) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 38
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    Biopolymers 5 (1967), S. 821-835 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical rotatory dispersion and ultraviolet absorption spectra of the 64 trinucleoside diphosphates containing the bases A, U, C, and G have been calculated by using a simple semiempirical approach. These calculations accurately predict the optical properties of the nine trimers for which extensive experimental results are available. The computed optical data should be useful in the identification of oligonucleotides obtained in the course of sequence determination of ribonucleic acids and should simplify the determination of the concentration of oligonucleotides in aqueous solution. Additional calculations indicate that it should be possible to analyze most, mixtures of sequence isomers of trinucleoside diphosphates by direct, measurement of the ORD of the mixture at neutral pH.
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  • 39
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    Biopolymers 5 (1967), S. 876-878 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 40
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    Biopolymers 5 (1967), S. 161-172 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equilibrium binding constants of Cd++ and Cu++ to native and denatured calf thymus DNA were determined polarographically. The binding constants are an exponential function of the potential at the binding site and as such they vary with ionic strength and with the charge on the DNA molecule. The correlation between the fraction of sites occupied by heavy metal ions and between the thermal stability of DNA in solution is discussed.
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  • 41
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    Biopolymers 5 (1967), S. 887-897 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complex shear viscosity η* = η′ - iη″ of poly (L-glutarmic acid) solution was measured by the torsional crystal method at 50 kc./sec. as a function of pH. A sharp peak was found at the midpoint of the helix-coil transition region in both η′ and η″. The relaxation time is calculated from η′ and η″ assuming a single relaxation process and the peak value at the midpoint of transition is estimated at 10-6 sec. Such behavior agrees well with the prediction from the theory of Schwarz. The attenuation of longitudinal sound waves at,3 Me./sec. was measured as a function of pH for solutions of poly(glutamic acid), glutamic acid, and gelatin. A small attenuation peak was observed for the three solutions, the peak height being almost, the same for them. The peak is interpreted in terms of the dissociation reaction of side chains.
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  • 42
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    Biopolymers 5 (1967), S. 915-919 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report the circular dichroism (CD) spectrum of poly-Lacetoxyproline in trifluoroethanol, a solvent in which the form I to form II conformational isomerization occurs slowly enough to permit observation of the spectral changes. A comparison is made to poly-Lproline. As judged by the similarity of the CD spectra, the conformations of the corresponding forms of the two polymers must be nearly the same. Transition assignments are proposed; these are shown to agree with the theoretical calculations of Pysh. There is a serious unexplained discrepancy between our solution data and those of Fasman for poly-Lacetoxyproline.
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  • 43
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    Biopolymers 5 (1967), S. 899-913 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dielectric relaxation of DNA solutions has been investigated with and without extraneous ions covering a wide frequency range. The effect of monovalent ions such as Na, K, and Li as well as divalent ions such as Mg, Ca, and Hg have been included in the study. These ions are found to have a profound effect on the dielectric increment and the relaxation time without affecting the molecular dimension drastically. This dielectric effect is interpreted as indicating the importance of counterion fluctuation on the low frequency dielectric constant of DNA in solution. The effect of an organic ion, tetra-methylammoniun bromide, has also been studied. This ion has no noticeable effect. A simple theory is derived on the basis of a microscopic model to account for the effect of external ions on the dielectric behavior of solutions of DNA.
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  • 44
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    Biopolymers 5 (1967), S. 236-241 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 45
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    Biopolymers 5 (1967), S. 243-249 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Block and random copolymers of γ-benzyl L-glutamate and glycine were studied by optical rotatory dispersion methods in order to ascertain the extent and stability of the α-helix formed by these polymers in appropriate solvent mixtures. Results indicate that when in solution such polymers do contain sections of α-helix. However, it appears that glycine does not readily fit into the α-helix which is largely due to the γ-benzyl L-glutamate segments. Further, there are indications that the helical sections in the random copolymers are due to the nonrandomness of the polymerization.
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  • 46
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is demonstrated that, poly(A + U) and poly(I + C) are both formed under low ionic strength conditions. Continuous variation studies indicate the formation of copper(II) complexes of poly A, poly C, and poly I, but not of poly U. Copper(II) in a 1:1 ratio to polynucleotide prevents the formation of poly(A + U) and brings about the dissociation of the poly (A + U) complex produced in the absence of the metal. Poly (I + C) is similarly dissociated by copper(II) ions. The addition of sufficient electrolyte reverses the copper(II) induced dissociation of poly(I + C). The effect of copper(II) on ordered synthetic polynucleotides is thus very similar to its effect on DNA.
    Additional Material: 7 Ill.
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  • 47
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    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 259-271 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and some of the physical-chemical properties of tricopolymers of L-glutamic acid, L-lysine, and L-alanine are reported here. The molar ratios of the glutamyl: lysyl: alanyl residues were 1:1:X or 3:2:X, where the alanyl content X was increased in regular steps. The α-helix content calculated from the optical rotatory dispersion of the polypeptides is compared with a predicted helix content estimated from the composition of the polymers and the known behavior of the homopolypeptides at pH 3, 8, and 12. At pH 3 copolypeptides containing 20 mole-% or more alanine exhibit a helix content equal to the sum of their alanyl and glutamyl residue contents. At pH 8 the helix content equals the alanyl content when the latter was 40 mole-% or higher; at lower alanyl contents the electrostatic interaction between charged glutamyl and lysyl residues makes some contribution. At pH 12 the amount of helix observed is proportional to the mole ratio of alanine residues present in the polymer. The helix content of a tricopolymer containing 1:1:3 mole ratios of glutamyl: lysyl: alanyl residues was determined in solutions of lithium bromide and in urea solutions. Both reagents led to a decrease in helix content at pH 3 and 8 to a minimum of approximately 20% helix in 8M urea or 5.5M LiBr. The helix-random chain transition curves at pH 3 and 8 are parallel when the urea concentration is varied, but differ in shape when the lithium bromide concentration is varied at pH 3 and 8. The mode of action of these two “denaturing” reagents may thus be different. Heating the same tricopolypeptide at pH 3 or 8 from 5 to 80°C. also led to a helix-random chain transition centered at approximately 45°C.
    Additional Material: 3 Ill.
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  • 48
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potentiometric titration curves of the silver(I) complexes of cytidine, adenosine, and uridine show little uptake of base below pH 7, unlike the curve for silver(I)-guanosine, which shows extensive base uptake at neutral pH. This observation is correlated with spectrophotometric data showing little difference between the silver complex spectra of adenosine, cytidine, and uridine and the spectra of uncomplexed nucleosides, except at high pH, but showing a great difference between the silver complex spectra of guanosine and inosine and the corresponding uncomplexed nucleosides even at pH 6. Similar comparisons of the silver complexes of poly A, poly C, poly I, and poly U, both by potentiometric titration and by spectrophotometry, show that poly I behaves like guanosine and inosine as expected, differing from poly A and poly C. However, poly U behaves like poly I and thus does not resemble uridine in its complexing behavior. There is thus a dichotomy between poly A and poly C on the one hand in silver complexing phenomena, compared with poly U and poly I on the other. When silver(I) is added to systems containing zinc(II) and various polynucleotides, the same dichotomy is noted. Silver(I) inhibits the degradation by zinc(II) of all four polynucleotides, but the degradation of poly I and poly U is prevented virtually completely. Silver(I) alone has no degradative effect on RNA and inhibits, the zinc(II) degradation of RNA. Polynucleotide complexes in which silver(I) and zinc(II) are simultaneously bound to different positions on the macromolecules are postulated as intermediates in the inhibited degradation reactions.
    Additional Material: 6 Ill.
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  • 49
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    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 325-326 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 50
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 71-78 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C-[2.4.6-Trimethoxy-phenyl]-N-[2.4.6-trinitro-phenyl]-nitrilimin (13) isomerisiert rasch zum 4.6-Dinitro-1-[2.4.6-trimethoxy-benzoyloxy]-benztriazol (22).
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  • 51
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 148-159 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dimeres Rhodiumdicarbonylchlorid und polymers Iridiumtricarbonylchlorid reagieren mit Kaliumdiphenylphosphid unter KCI-Abspaltung und Bildung von Carbonylkomplexen mit μ-Phosphido-Brücken. [(CO)2RhPR2]n und [(OC)3IrPR2]2 (R = C6H5). Die Einwirkung von Tetraphenyldiphosphin und -diarsin, R2EER2(E = p, As), auf [Rh(CO)2CI]2 führt über instabile Komplexe CI(OC)Rh(E2R4)2 zu dimeren Verbindungen vom Typ [CI(OC)RhER2]2, von denen die cis-trans-Isomeren isoliert werden können. Auch die entsprechenden Iridiumverbindungen wurden über den Pyridinkomplex CI(OC)2Irpyr erhalten.Alkylendiphosphine liefern mit [Rh(CO)2CI]2und CI(OC)2Ir pyr zunächst ohne CO-Abspaltung zweikernige, instabile Komplexe vom Typ CI(OC)2MeR2P - [CH2]N - PR2Me(CO)2CI(Me = Rh, IR; R = C6H5;n = 1 und 2). Mit einem überschuß der Phosphine entstehen die Neutralkomplexe CI(OC)Rh(R2P)2C2H4 und [CI(OC)Rh(R2P)2 CH2]n sowie die kationischen Komplexe [Rh {R2P)2C2H4)}2]X und [OCIr{(R2P)2CH2}2]X (X = Cl, PF6).
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  • 52
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 35-46 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3.4-Dihydroxy-phenäthylamin reagiert im Gegensatz zu anderen primären aliphatischen Aminen mit Acetessigaldehyd nicht nur zum entsprechenden 2-Methyl-5-acetyl-pyridiniumsalz (1), sondern außerdem unter dehydrierender Verknüpfung von Benzol- und Pyridinring zu einem 6.7-Dihydro-benzo[a]chinoliziniumsalz (2), dessen Methyl- und Acetyl-Seitenkette sich in „natürlicher“ Stellung befinden. Der vollaromatische Ring C von 2 läßt sich mit Natriumborhydrid hydrieren (8, 11), Ring B mit Tetrachlor-o-benzochinon dehydrieren (13, 14), die Acetyl-Seitenkette in eine Äthylgruppe umwandeln (9, 10); mit Allylbromid werden insgesamt vier Allylreste eingeführt. - Fragen des Reaktionsverlaufs, der Spektren sowie der Verwandtschaft zu Alkaloiden werden erörtert.
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  • 53
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 79-92 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Der Verlauf massenspektrometrischer Abbaureaktionen ist von der durchschnittlichen Angregungsenergie der Molekül-Ionen abhängig. Diese setzt sich aus der vom angreifenden Elektron auf das Molekül übertragenen, das Ionisierungspotential überschreitenden Energiemenge, und der thermischen Anregung der Moleküle vor der Ionisation zusammen. Durch Verminderung dieser Anregungsenergie können mehrstufige massenspektrometrische Abbauprozesse auf Zwischenstufen abgefangen werden, wodurch ein besserer Einblick in den Zerfallsmechanismus gewährleistet wird. Grundlagen und Anwendungsbereich dieser Methode werden am Beispiel aliphatischer Äther erläutert.
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  • 54
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 107-112 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ausgehend von Acetylencarbonylverbindungen werden einige disubstituierte Thiophen-Derivate (1-3) dargestellt. Weiterhin wird die Reaktion von Polyinen mit Natriumdisulfid untersucht. Als Hauptprodukte erhält man Dithiacyclopenten-Derivate (8, 15-17). Die Eigenschaften dieser Substanzklasse werden diskutiert.
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  • 55
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Synthese linearer Furanoxanthone (5-Oxo-5H-furo[3.2-b]xanthene) aus 2-Hydroxy-3-acetyl-xanthonen wird an den Beispielen 5-Oxo-3-methyl- und 5-Oxo-3.7-dimethyl-5Hfuro[3.2-b]xanthen (4a, b) beschrieben.
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  • 56
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die IR-Spektren m- und p-substituierter Phenylessig- und Phenylglyoxylsäuren werden im Bereich der Carbonyl-und Hydroxylbanden verglichen. Die streng proportionalen Frequenzverschiebungen von α-Carbonyl- und Hydroxylbanden im Falle der chelatisierten Phenyl-glyoxylsäuren zeigen, daß die Wasserstoffbrücke zum π-Elektronenpaar der Carbonylgruppe gebildet wird, und daß sowohl induktive wie konjugative Effekte über intramolekulare Wasserstoffbrücken mit hoher Empfindlichkeit vom Protonenacceptor zum -donator übertragen werden.
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  • 57
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 448-455 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die stellungs- und konfigurationsisomeren n-Octene wurden mit konz. Schwefelsäure sulfatiert und die Isomerenverteilung sowohl in den sich bildenden Alkylsulfaten als auch in dem nicht umgesetzten Olefin bestimmt. Läßt man das Olefin mit einem Unterschuß oder höchstens mit der äquimolaren Menge an Schwefelsäure so reagieren, daß die Schwefelsäure dem Olefin zugefügt wird, bilden sich vornehmlich die aufgrund der Doppelbindungslage im eingesetzten Olefin zu erwartenden Alkylsulfat-Isomeren. Wird hingegen das Olefin der Säure zugefügt bzw. ist diese am Ende im Überschuß vorhanden, so bildet sich unabhängig von der Doppelbindungslage und der Konfiguration des Ausgangsolefins stets das gleiche Isomerengemisch sekundärer Alkylsulfate. Das Ausmaß der Bindungsisomerisierung im nicht umgesetzten Olefin entspricht etwa der Isomerenverteilung im Sulfatestergemisch.
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  • 58
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 694-697 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 59
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 736-740 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Synthese der Tetrazolylmercapto-essigsäure-azide 5a-c und Tetrazolylmercaptomethyl-isocyanate 6a-c wird beschrieben.
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  • 60
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 748-754 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Reaktion von (CH3)3SiN3 mit SnCl4 erhält man über eine unter bestimmten Bedingungen isolierbare Zwischenverbindung Cl3SnN3 (CH3)3SiN3 als Endprodukt [Cl2Sn(N3)2]n. Einige Eigenschaften und das Infrarotspektrum der Verbindungen sowie Strukturvorschläge werden beschrieben.
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  • 61
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 795-801 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Dehydrierung von Phorbol und Phorbol-f-ol sowie die Dehydratisierung von Phorbol-f-ol führt zu Azulenen. Dies deutet darauf hin, daß Phorbol möglicherweise eine Hydroazulen-Struktur enthält.
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  • 62
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 624-628 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1.3-Dioxolan (1a) und 2-Alkyl-1.3-dioxolane (1b-f) sind sehr leicht peroxygenierbar. Als Primärprodukte der Peroxygenierung wurden die Hydroperoxide (2a-f) isoliert. Diese gehen durch Hydrierung quantitativ in Glykolhalbester über. Unter den Bedingungen der Vakuumdestillation bilden sich die dimeren Peroxide (5) und H2O2.
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  • 63
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 690-691 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 64
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 701-703 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 65
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 537-541 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die bisher untersuchten Arten des Tribus Helenieae zeigen, daß die botanische Unterteilung dieses Tribus gut mit den gefundenen Inhaltsstoffen übereinstimmt. Neben bereits bekannten Polyinen werden einige neue Verbindungen (1,2,6,10) isoliert, die sich biogenetisch von dem weitverbreiteten Pentainen 3 ableiten.
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  • 66
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 542-546 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Umsetzung von Dehydrochinolizidin (2) mit dem Hexadienon 1 liefert ein tricyclisches Keton (3), das in der Enolform 4 vorliegt und äußerst leicht in ein Diketon (10) übergeht.
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  • 67
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 564-577 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In den 2-Thio-hydantoin-Derivaten 2 von Asparagin-, Glutamin- und α-Amino-adipinsäure kann das Ringsystem als kombinierte Schutzgruppe für die α-Amino- und die benachbarte Carboxyl-Funktion betrachtet werden. Am noch freien Carboxyl können die Verbindungen 2 mit Aminosäureestern Peptidverknüpfungen eingehen. Dies kann auf konventionelle Weise erfolgen, während beim Glutamin- und α-Amino-adipinsäure-Derivat die zugehörigen Lactame 3 als ω-carboxylaktivierte Formen fungieren können. Die Entschwefelung der Thio-hydantoin-ω-peptide 5 mit Raney-Nickel liefert ω-Peptidester, die in Form der α-Formamino-carbonamide 4 anfallen. - Ungesättigte, methylverzweigte 2-Thio-hydantoin-peptidester 8 lassen sich analog aus den Kondensationsprodukten 7 von 2-Thio-hydantoin mit Brenz-traubensäure, Acetessigsäure-äthylester oder Lävulinsäure gewinnen. Die Entschwefelung bietet eine Möglichkeit zur Synthese β-methylverzweigter Analoger der erwähnten ω-Peptidester (Beispiel 8b). - Aus optisch aktiver Pyroglutaminsäure und N-Benzoyl-L-alanin können zwar aktive Thiohydantoin-Derivate dargestellt werden, jedoch racemisieren diese leicht. - Die Entschwefelung von 4-Cyclohexylimino-5.5-dimethyl-2-thio-hydantoin (14, R = R′ = CH3, R″ = c-C6H11) liefert 4-Cyclohexylimino-5.5-dimethyl-4.5-dihydro-imid-azol (17).
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  • 68
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1200-1205 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Strukturen und Konfigurationen einiger natürlicher Schwefelverbindungen (2, 3, 4, 26 bis 28) werden durch Synthese gesichert.
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  • 69
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1206-1208 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Wurzeln von Serratula radiata Bieb. enthalten neben dem weitverbreiteten En-tetrain-en 1, mehrere Thiophenverbindungen, von denen drei (5, 7, 8) bisher noch nicht bekannt waren. Die Strukturen werden durch die physikalischen Daten sowie durch einige Reaktionen geklärt.
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1245-1247 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acetessigsäure-äthylester wird an der Methylengruppe leicht nitrosiert. Auf die Explosionsgefahr bei der Reinigung des Reaktionsproduktes durch Hochvakuumdestillation wird jedoch nirgendwo hingewiesen. Am tert.-Butylester wird der Zerfallsmechanismus untersucht.
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  • 71
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3283-3288 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nach weiteren Untersuchungen über Derivate, besonders aktivierter Ester, und Peptide von NHPhe wurde ausgehend vom C-terminalen Tetrapeptid 5 mit Hilfe des Boc-NHPhe-hydroxysuccinimidesters (2c) das [5-Asparagin, 7-L-α-Hydrazino-β-phenyl-propionsäure]Eledoisin-(4-11)-Octapeptid (als Bis-trifluoracetat9b) nach der Nitrophenylester-Methode aufgebaut.
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  • 72
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3371-3384 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Addition von Dichlormethyllithium (20) und verschiedener olefinischer Carbenoide (8,24,30) an Triphenylbor führt zu α-chlorierten Lithium-boraten, die unter „inverser Stevens-Umlagerung“ zu Boranen und Lithiumchlorid thermolysiert werden. Die Substitution des α-Halogens durch Bor-ständiges Phenyl verläuft stereospezifisch unter Konfigurationsumkehrung und wird als Synchronprozeß interpretiert. Ein zweites Halogen in α-oder β-Stellung veranlaßt Folgereaktionen am umgelagerten Boran.
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1778-1785 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die magnetische Protonenresonanz der substituierten Diaziridine 2-81) zeigt, daß der gesättigte C—N—N-Dreiring ein Asymmetriezentrum darstellt. Die Inversion an mindestens einem der beiden Stickstoffatome verläuft demnach verhältnismäßig langsam. Die freie Enthalpie der Aktivierung muß bei einigen der untersuchten Verbindungen größer als 21 kcal/ Mol sein.
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1802-1813 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die chemischen Verschiebungen der Ringprotonen von 36 substituierten 1.3-Diphenyl-Δ2-pyrazolinen und von 23 substituierten 3-Phenyl-Δ2-isoxazolinen werden mit denen der Stammkörper verglichen. Die Methode der kleinsten Fehlerquadrate führt zu den Parametern Δτ für gem., cis-vic. und trans-vic. Substituenten. Diese Substituenteneffekte werden theoretisch diskutiert und sind von diagnostischem Wert bei der Strukturermittlung.
    Additional Material: 3 Ill.
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3413-3417 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Addition von Vinyldiazomethan an Chinone werden 3-Vinyl-pyrazolochinone (1-4) dargestellt. Ihr chemisches Verhalten wird untersucht.
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  • 76
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3432-3437 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dreizehn neue Verbindungen des Typs 4-F—C6H4—X, mit X = PH2, P(CH3)2, P(C6H5)2, P(O)(C6H5)2, P(O)(CH3)2, P(O)(OC2H5)2, P(S)Cl2, P(S)(C6H5)2, P(CH6)3J, P(C6H4F)2, P(O)(C6H4F)2, P(S)(C6H4F)2 und P(CH3)(C6H6H4F)2J wurden dargestellt. Von den genügend löslichen Substanzen sowie von 4-F—C6H4—PCI2 und 4-F—C6H4—P(O)Cl2 wurden die 19F-NMR-Spektren aufgenommen, die chemischen Verschiebungen, bezogen auf Fluor-benzol, bestimmt und daraus die Hammettschen σp-Konstanten der phosphorhaltigen Substituenten berechnet. Damit war zum ersten Mal ein quantitativer Vergleich der PH2-mit der NH2-Gruppe möglich. Alle diese Substituenten sind Elektronenakzeptoren, der stärkste gemessene Akzeptor ist die P(O)Cl2- und der schwächste die P(CH3)2-Gruppe.
    Additional Material: 3 Tab.
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  • 77
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3454-3456 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 78
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3463-3465 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 79
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1845-1849 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Perjodatoxydation von 3-[β-D-Glucopyranosyl]-thymin und anschließende Nitromethan-Cyclisierung führt zu einem Gemisch von 3-[3-Nitro-3-desoxy-hexopyranosyl]-thyminen, aus dem durch Schichtchromatographie das gluco-Isomere 3 abgetrennt wurde. Katalytische Hydrierung liefert 3-[3-Amino-3-desoxy-β-D-glucopyransoyl]-thymin (5). Die Konfigurations-zuordnung ergab sich aus NMR-spektroskopischen Daten des Tri- und Tetraacetats (6 bzw. 4).
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  • 80
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1833-1844 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ausgehend von 7-[β-D-Ribofuranosyl]- (1) bzw. 7-[β-D-Glucopyranosyl]-theophyllin (3) wurde durch Perjodatoxydation und anschließende Nitromethan-Cyclisierung ein Gemisch von 7-[3-Nitro-3-desoxy-hexopyranosyl]-theophyllin-Isomeren erhalten. Durch fraktionierte Kristallisation ließen sich die gluco-, manno- und galakto-Verbindungen (6, 4, 5) trennen. Katalytische Hydrierung führte zu den entsprechenden [3-Amino-3-desoxy-β-D-hexopyranosyl]-theophyllin-Nucleosiden (9, 7, 8), die als Hydroacetate, N-Acetate und Tetraacetate charakterisiert wurden. Die Konfigurationszuordnung ergab sich aus vergleichender Papierchromatographie, NMR-spektroskopischen Daten und chemischen Identifizierungsreaktionen.
    Additional Material: 2 Ill.
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  • 81
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1850-1857 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Alkali-Einwirkung auf 2.4.6-Triphenyl-o-chinolacetat (3) in Gegenwart von Luftsauerstoff entsteht ein farbloses Dimeres des 3.5-Diphenyl-2-benzoyl-cyclopentadienons (8) der Konstitution 9a oder 9b. Dieses steht in Lösung mit seinem roten Monomeren in einem temperaturabhängigen Gleichgewicht, zeigt also Thermochromie. Unter Sauerstoffausschluß bildet sich aus o-Chinolacetat 3 das entsprechende vollständig enolisierte Diphenyl-benzoyl-cyclopentenon 5. Reaktionen, IR- und NMR-Spektren werden beschrieben.
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  • 82
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3460-3462 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 83
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Darstellung von 1.1-Dihalogen-cyclopropanen aus Olefinen, Trihalogenmethan und Äthylenoxid in Gegenwart eines salzartigen Katalysators wird beschrieben. Die Reaktionen werden über intermediär gebildetes Dichlor-, Fluorchlor- und Difluorcarben formuliert.
    Additional Material: 5 Tab.
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1892-1897 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eine modifizierte Friedel-Crafts-Acylierung am Δ3-Caren ergibt in hohen Ausbeuten 3-Acyl-Δ4-carene. Diese Verbindungen ermöglichen die Synthese zahlreicher 3-substituierter Derivate des Δ3-Carens, des Carans und des Δ4-Carens.
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  • 85
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1874-1891 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: S.S'-Dialkyl-dithiobiurete (1), durch Alkylierung von Dithiobiuret gut zugänglich, eignen sich als Ausgangsstoffe für eine einfache Synthese von 1.3.5-Triazinen, die mehrere funktionelle Gruppen enthalten. Mit Carbonsäurechloriden lassen sich in einem Reaktionsschritt 2-substituierte 4.6-Bis-alkylmercapto-1.3.5-triazine (2, 4) darstellen, die mit Hydroperoxid in die 4.6-Dihydroxy- (12) und mit Chlor in die 4.6-Dichlor-1.3.5-triazine (13) übergeführt werden können. Die Anwendung der neuen Synthese auf S-Alkyl-guanyl-isothiuronium-salze (8) und Imino-bis-[carbimidsäure-phenylester] (10) führt zu 2-substituierten 4-Amino-6-alkylmercapto-(9) bzw. 4.6-Diphenoxy-1.3.5-triazinen (11).
    Additional Material: 7 Tab.
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  • 86
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3664-3670 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Chlor-5-cyan-pyrimidin (3) gibt mit Ammoniak, prim. und sek. Aminen, Hydrazinen, Natriumalkoholaten sowie Natriummercaptiden unter Substitution des 4-Chlor-Atoms die Derivate 4-14. Durch katalytische Reduktion des 4-Amino- und 4-Hydroxy-5-cyan-pyrimidins erhält man den bisher nicht bekannten 4-Amino- und 4-Hydroxy-pyrimidin-aldehyd-(5) (18 und 17).
    Additional Material: 2 Tab.
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  • 87
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3679-3682 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Produkte der Addition von Tetramethylthioharnstoff an Acetylendicarbonsäure-di-methylester in Dioxan als Solvens werden beschrieben, die Konstitutionen aufgeklärt und ihre Bildung diskutiert.
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  • 88
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3689-3697 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Jod-Oxydation von Tetramethoxy-äthylen (1) ergab Dimethyloxalat (4) und Tetramethoxy-bernsteinsäure-dimethylester (6). Durch Oxydation in Gegenwart von Natriummethylat ließ sich dabei die Zwischenstufe des Tetramethoxy-äthylen-Dikations 3 zu Hexamethoxyäthan (7) abfangen. Die Reduktion weiterer Verbindungen mittels Tetramethoxy-äthylen wurde untersucht.
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  • 89
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3716-3724 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An Perchlorallen (1) lassen sich im Temperaturbereich von -75 bis -30° Brom und Chlorjod sowie in Gegenwart von AICI3 Chlorwasserstoff und aliphatische Säurechloride addieren, ohne daß die Dimerisation zu 2 merklich in Erscheinung tritt. Die Additionsrichtung der unsymmetrischen elektrophilen Agenzien, die geklärt wird, deutet auf eine hohe Elektronendichte am C-2 des Allens hin. Im Zuge der Konstitutionsaufklärung des aus Acetylchlorid und 1 gebildeten Methylketons 8a werden einige hochchlorierte Ketone (9) und Carbonsäuren (11, 12, 13) beschrieben. Das Allendimere 2 reagiert mit Diazomethan bei 0° unter N2-Abspaltung zu dem Spiran 17 mit Cyclopropanring.
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  • 90
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1927-1935 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wurzeln und oberirdische Teile von Chrysanthemum carinatum Schousb. enthalten zahlreiche neue Acetylenverbindungen, deren Strukturen weitgehend geklärt werden (7, 8, 33, 34, 35, 37). Die Pflanze enthält vor allem Spiroketal-enoläther-polyine mit Methylmercaptogruppe, die nur zum Teil bekannt sind. Daneben lassen sich jedoch auch zwei neue Benzolderivate (9, 30) isolieren.
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  • 91
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 1915-1926 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus den Wurzeln verschiedener Vertreter des Tribus Cynareae werden mehrere sehr polare Polyine isoliert und deren Strukturen geklärt. In allen Fällen handelt es sich um C17-Alkohole, die mit l-Rhamnose bzw. ihren Acetaten glykosidisch verknüpft sind (8, 9). Auch das Aglykon kommt in kleiner Menge natürlich vor. Die oberirdischen Teile von Serratula gmelini Ldb. enthalten ein Gemisch von C15—C18-Aldehyden (neu 23 und 25) mit verschiedenen chromophoren Systemen, die die nahe Verwandtschaft mit der Gattung Centaurea erkennen lassen.
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  • 92
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3627-3643 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Autoxydationsgeschwindigkeit alkylsubstituierter Hydrochinone zeigt die erwartete Abhängigkeit vom Redoxpotential: log k1—logk2 = a-(E1—E2). Kinetische Messungen der Autoxydation von Brenzcatechin-, Hydroxy-hydrochinon- und Resorcinderivaten werden im Zusammenhang mit ihrem Potential diskutiert.
    Additional Material: 6 Ill.
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  • 93
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3777-3781 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Versuche zur Darstellung von Halogendialkoxymethanen gaben stets nur deren Spaltprodukte. Die Nacharbeitung eines in der Literatur beschriebenen Verfahrens zur Darstellung von Bromdimethoxymethan (4) durch Bromierung von Dimethoxyessigsäure führte unter intramolekularer Methylwanderung zu Oxalsäure-dimethylester und nicht zu 4.  -  Durch Bromierung von O-Methyl-mandelsäuren bzw. deren Estern sind in sehr guten Ausbeuten die entsprechenden Arylglyoxylsäurederivate zugänglich.
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  • 94
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3789-3794 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus NaCN und NF3 entsteht im Nickelrohr bei 300-320° quantitativ (CN)2. Sind bei 400° die Verweilzeiten von NF3 kurz, dann lassen sich (CN)2, (FCN)3, F3C—N=N—CF3, CF4 und höhere CnF2n+2-Verbindungen, isolieren. Mit länger werdender Verweilzeit steigt der Anteil an (FCN)3 und C—F-Verbindungen, während die anderen Fluoride verschwinden. Mit einem geringen Überschuß von NF3 gibt CICN bei 450-500° wechselnde Mengen an F3C—N=N—CF3 neben (FCN)3, F3C—N=CF2 und Cl2. Aus äquimolaren Mengen von NF3 und F3C—CN erhält man bei 515° F3C—NF2 neben CF4, C2F6 und (FCN)3 — F3C—CN und N2F4 (1:1) setzen sich im Autoklaven bei 220° zu (F3C—CN)3 um; bei der UV-Bestrahlung tritt dagegen F3C—CF2—NF2 auf. CICN und N2F4 reagieren bei UV-Bestrahlung zu CF3CI, CF2Cl2 und CF4.
    Additional Material: 2 Tab.
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  • 95
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3808-3813 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diels-Alder-Synthesen von Hexachlor-cyclopentadien mit geminalen Dichlor-, Fluor-chlor-und Difluor-cyclopropanen, die eine ungesättigte Seitenkette besitzen, werden beschrieben. Beim 1.2.3.4.7.7-Hexachlor-5-[2.2-dichlor-1-methyl-cyclopropyl]-bicyclo[2.2.1]-hepten-(2) (9) werden die Stereoisomeren getrennt und mit Hilfe der NMR-Spektren zugeordnet.
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  • 96
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    Berichte der deutschen chemischen Gesellschaft 100 (1967) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 97
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3835-3837 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ausgehend von Cyclodecadien-(1t.5c) konnte Cyclodecanon durch Epoxydation und anschließende hydrierende Isomerisierung in guter Ausbeute erhalten werden.
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  • 98
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3861-3868 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Struktur der aus Echinacea-Arten sowie aus Chrysanthemum frutescens isolierten Isobutylamide wird durch Synthese endgültig gesichert.
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  • 99
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3877-3892 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phenyllithium spaltet aus cis- und trans-Styrylchlorid Chlorwasserstoff nach einem neuartigen Eliminierungstyp (E2cB) ab: Primär wird der zum Chlor α-ständige Wasserstoff metalliert, sodann wird das Zwischenprodukt unter der Einwirkung einer zweiten Molekel Base dehydrochloriert. Phenylacetylen tritt intermediär nicht auf.
    Additional Material: 5 Ill.
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  • 100
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    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 3937-3943 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In Rhamnus frangula L. ließen sich sechs nur in äußerst geringer Menge vorkommende Alkaloide nachweisen. Das als Frangulanin bezeichnete Hauptalkaloid wurde isoliert. Frangulanin ist aus einer p-Hydroxy-styrylamin-Einheit und den Aminosäuren Leucin, β-Hydroxy-leucin und N.N-Dimethyl-isoleucin aufgebaut. Aufgrund seiner spektroskopischen Daten und der massenspektrometrischen Fragmentierung kommt ihm die Struktur .
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