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  • 1965-1969  (128)
  • 1920-1924
  • 1850-1859
  • Physical Chemistry  (56)
  • Psychopharmacology  (37)
  • Insulin  (35)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Acta diabetologica 6 (1969), S. 197-205 
    ISSN: 1432-5233
    Keywords: Diurnal variations ; Food intake ; Glucose load ; Insulin ; Tolbutamide test
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume On a étudié l'effet de la lumière et de la période d'ingestion des aliments sur l'élimination d'insuline par les urines. On peut démontrer l'existence d'un rythme circadien et la présence de deux facteurs de régulation pour cette élimination. On présente quelques hypothèses concernant ces phénomènes.
    Abstract: Resumen Se estudió el efecto que sobre la eliminación de insulina urinaria ejercen los períodos de luzoscuridad y el horario de administración del alimento. Se demuestra la existencia de un ritmo circadiano de eliminación de dicha hormona, describiéndose dos reguladores del mismo. Se hacen especulaciones fisiopatológicas acerca de su significado.
    Notes: Riassunto E' stato studiato l'effetto della luce e del periodo di ingestione del cibo sull'eliminazione di insulina nelle urine. Si può dimostrare l'esistenza di un ritmo circadiano e la presenza di due fattori di regolazione per questa eliminazione. Vengono presentate alcune ipotesi concernenti questi fenomeni.
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  • 2
    ISSN: 1432-5233
    Keywords: Glybenclamide ; Insulin ; Insulin secretion ; Sulfonylureas ; Tolbutamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Les effets métaboliques de la glybenclamide et de la tolbutamide ont été étudiés chez deux groupes de sujets normaux traités avec des doses comparables des deux sulphanylurées. En rapport aussi à la dose de 1:400, la glybenclamide a démontré une activité insuline-sécrétive bien majeure de celle de la tolbutamide. La réponse insulinique a été suivie par une rapide et prolongée diminution des NEFA sériques et par un moins persistant effet hypoglycémique. Les effets métaboliques de l'HB 419 sont encore évidents 10–12 heures après l'administration du médicament, tandis que l'activité de la tolbutamide est terminée géneralement entre 4–6 heures. Quand l'administration des médicaments a été pratiquée en concomitance avec une charge veineuse de glucose, le coéfficient de Conard était élevé d'une façon significative par toutes les deux sulphanylurées.
    Abstract: Resumen Los efectos metabólicos de la glibenclamida y de la tolbutamida han sido investigados en dos grupos de sujetos normales tratados con dosis comparables de las dos sulfanilúreas. Inclusive en una relación de dosificación de 1:400, la glibenclamida ha demostrado una actividad insulinosecretora mucho mayor de la tolbutamida. La respuesta insulínica ha sido seguida de una disminución pronta y prolongada de los NEFA séricos y de un efecto hipoglucemiante menos persistente. Los efectos metabólicos del HB 419 son aún evidentes a las 10–12 horas después de la administración del medicamento, mientras la actividad de la tolbutamida es anulada por lo general dentro de 4–6 horas. Cuando la suministración de los medicamentos ha sido practicada en coincidencia con una carga venosa de glucosa, el coeficiente de Conard apareció significativamente elevado por ambas sulfanilúreas.
    Notes: Riassunto Gli effetti metabolici della glibenclamide e della tolbutamide sono stati indagati in 2 gruppi di soggetti normali trattati con dosi comparabili delle due sulfaniluree. Anche in un rapporto di dosaggio di 1:400, la glibenclamide ha mostrato un'attività insulino-secretiva assai maggiore di quella della tolbutamide. La risposta insulinica è stata seguita da una pronta e prolungata diminuzione dei NEFA serici e da un meno persistente effetto ipoglicemico. Gli effetti metabolici del-l'HB 419 sono ancora evidenti 10–12 h dopo la somministrazione del farmaco mentre l'attività della tolbutamide si annulla generalmente entro 4–6 h. Quando la somministrazione dei farmaci è stata praticata in coincidenza con un carico venoso di glucosio, il coefficiente di Conard è apparso significativamente innalzato da entrambe le sulfaniluree.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Acta diabetologica 6 (1969), S. 371-388 
    ISSN: 1432-5233
    Keywords: Insulin ; Insulin antibodies ; Insulin assay ; Laboratory technique
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1432-5233
    Keywords: Insulin ; Insulin antibodies ; Islets of Langerhans ; Placenta ; Transport
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Ce travail est la continuation des communications préliminaires sur la résistance insulinique des nouveaux-nés de mères insuline-résistantes. Les recherches ont été conduites sur cobayes et sur sujets humains. Les AA. ont démontré que les anticorps anti-insuline passent dans la circulation fœtale et provoquent l'apparition d'une insuline-résistance passive qui va disparaître dans les premières semaines de la vie. Les anticorps contre l'insuline bovine lient en partie l'insuline endogène des cobayes, ce qui est mis en evidence par l'hyperglycémie élevée des cobayes jeunes nées de mères insuline-résistantes. Les anticorps anti-insuline n'ont aucun effet important sur la structure du pancréas des cobayes dans la période périnatale.
    Abstract: Resumen Este trabajo representa la continuación de las comunicaciones preliminares sobre la resistencia insulínica que presentan las personas nacidas de madres insulino-resistentes. Las investigaciones han sido efectuadas en cobayas y hombres. Se ha demostrado que los anticuerpos anti-insulina pasan al círculo fetal, provocando la aparición de insulino-resistencia pasiva, que desaparece durante las primeras semanas de vida. Los anticuerpos contra la insulina bovina ligan en parte la insulina endógena de cobayas, como lo demuestra la hiperglucemia elevada de las cobayas jóvenes nacidas de madres insulino-resistentes. Los anticuerpos anti-insulina no ejercen ningún efecto apreciable sobre la estructura del páncreas de las cobayas durante el período peri-natal.
    Notes: Riassunto Questo lavoro rappresenta la continuazione delle comunicazioni preliminari sulla resistenza insulinica dei nati di madri insulino-resistenti. Le ricerche sono state condotte su cavie e su uomini. E' stato dimostrato che gli anticorpi anti-insulina passano nel circolo fetale inducendovi la comparsa di una insulino-resistenza passiva che scompare nelle prime settimane di vita. Gli anticorpi contro l'insulina bovina legano in parte l'insulina endogena di cavie, come è evidenziato dall'elevata iperglicemia delle cavie giovani nate da madri insulino-resistenti. Gli anticorpi anti-insulina non esercitano alcun effetto di rilievo sulla struttura del pancreas delle cavie nel periodo perinatale.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Acta diabetologica 6 (1969), S. 796-808 
    ISSN: 1432-5233
    Keywords: Desensitization ; Immunoglobulins ; Insensitivity ; Insulin ; Insulin allergy ; Insulin antibodies ; Macroglobulins ; Porcine insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Cinq patients atteints d'allergie à l'insuline ont été désensibilisés par de l'insuline de porc selon la méthode d'Urbach et Gotlieb. Le diagnostic d'allergie à l'insuline a été posé sur la base des manifestations cliniques, de la positivité des réactions cutanées et, dans 2 cas, des réactions de Prausnitz-Küstner (P.K.). On a obtenu dans 3 cas une désensibilisation. La présence d'anticorps anti-insuline a été révélée par la méthode immunoautoradiographique en employant de l'insuline131J. Avant la désensibilisation la présence d'anticorps IgG a été enregistrée chez 3 patients tandis que chez 2 on a démontré également des anticorps IgA. Une réaction de P.K. positive a été observée chez des patients dont les sérums contenaient des anticorps IgA. Pendant la désensibilisation on a observé une apparition transitoire de macroglobulines capables de lier l'insuline131J. Après la désensibilisation on a constaté la persistance de la positivité aux réactions cutanées immédiates à l'insuline de porc et de boeuf. En même temps les réactions retardées et la réaction de P.K. à l'insuline de porc étaient interverties, bien que les mêmes réactions à l'insuline bovine restaient positives.
    Abstract: Resumen Cinco pacientes que padecían de alergia a la insulina han sido desensibilizados con insulina porcina según el método de Urbach y Gotlieb. El diagnóstico de alergia a la insulina ha sido puesto teniendo en cuenta las manifestaciones clínicas, el positivismo de las reacciones cutáneas, y, en 2 casos, las reacciones de Prausnitz-Küstner (P.K.). En 3 casos se ha obtenido desensibilización. La presencia de anticuerpos anti-insulina ha sido puesta en evidencia con el método inmunoautoradiográfico, empleando insulina131J. Antes de la desensibilización, la presencia de anticuerpos IgG ha sido hallada en 3 pacientes, mientras que en 2 han sido demostrados también anticuerpos IgA. Una reacción de P.K. positiva ha sido observada en pacientes cuyos sueros contenían anticuerpos IgA. Durante la desensibilización se ha observado aparición transitoria de macroglobulinas capaces de ligar la insulina131J. Al cabo de la desensibilización se ha notado la persistencia del positivismo a las respuestas cutáneas inmediatas a la insulina porcina y bovina. Al mismo tiempo, las respuestas retardadas y la reacción de P.K. a la insulina porcina cstaban invertidas, no obstante que las mismas reacciones a la insulina bovina hubieran quedado positivas.
    Notes: Riassunto Cinque pazienti con allergia all'insulina sono stati desensibilizzati con insulina suina secondo il metodo di Urbach e Gotlieb. La diagnosi di allergia all'insulina è stata posta sulla base delle manifestazioni cliniche, della positività delle reazioni cutanee e, in 2 casi, delle reazioni di Prausnitz-Küstner (P.K.). In 3 casi si è ottenuta una desensibilizzazione. La presenza di anticorpi anti-insulina è stata rivelata con il metodo immunoautoradiografico impiegando insulina131J. Prima della desensibilizzazione la presenza di anticorpi IgG è stata riscontrata in 3 pazienti mentre in 2 sono stati dimostrati anche anticorpi IgA. Una reazione di P.K. positiva è stata osservata in pazienti i cui sieri contenevano anticorpi IgA. Durante la desensibilizzazione si è osservata una comparsa transitoria di macroglobuline capaci di legare l'insulina131J. Dopo la desensibilizzazione si è riscontrata la persistenza della positività delle risposte cutanee immediate all'insulina suina e bovina. Al tempo stesso le risposte ritardate e la reazione di P.K. all'insulina suina erano invertite, sebbene le stesse reazioni all'insulina bovina rimanessero positive.
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  • 6
    ISSN: 1432-1912
    Keywords: Amiloride ; Insulin ; Glucose Transport ; Leucine Incorporation ; Isolated Adipose Tissue ; Amilorid ; Insulin ; Glucosetransport ; Leucineinbau ; isoliertes Fettgewebe
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung 1. Die Aufnahme von Glucose ins isolierte epididymale Fettgewebe und die Bildung von 14CO2 aus [1-14C]-Glucose wurde als Maß von Transportvorgängen, die Incorporation von [1-14C]-Leucin ins Fettgewebsprotein als Maß der Proteinsynthese vor und nach Zusatz von Amilorid in vitro verwendet. 2. Amilorid setzt den Transport durch die Membran sowohl ohne als auch mit Stimulierung durch Insulin halbmaximal in 10−4 M-Konzentration herab. Aus der Kinetik des Transportes kann geschlossen werden, daß Amilorid die maximale Geschwindigkeit des gesamten Vorganges verlangsamt, ohne die Transportkonstante zu verändern. 3. Der Einbau von Leucin ins Fettgewebsprotein wird durch Amilorid in 3 · 10−4 M-Konzentration auf ein Zehntel herabgesetzt. Das Verhalten von [1-14C]-α-Aminoisobuttersäure läßt den Schluß zu, daß der Aminosäuretransport durch die Membran des Fettgewebes nicht beeinflußt wird. 4. Die Wirkungen des Amilorids am Fettgewebe entsprechen im Prinzip denjenigen des Triamterens und des 6-Aminonicotinsäureamids. Ebenso ist allen gemeinsam, daß sie den renalen Natrium- und Kaliumtransport im distalen Abschnitt des Nephrons hemmen. 5. Es ist möglich, daß ein Zusammenhang zwischen den hemmenden Wirkungen dieser Pharmaka auf den Leucin-Einbau in das Fettgewebsprotein und der Störung von Transportvorgängen durch biologische Membranen besteht.
    Notes: Summary 1. The uptake of glucose and the formation of 14CO2 from [1-14C]-glucose were used as a measure of transport processes, and the incorporation of [1-14C]-leucine into the protein of adipose tissue served as a measure of protein synthesis before and after the addition of amiloride to the isolated epididymal adipose tissue of the rat in vitro. 2. In a concentration of 10−4 M, amiloride decreases the glucose transport through tissue membranes by 50% with and without stimulation by insulin. It can be deduced from the kinetics of the transport that amiloride slows down the maximal velocity of the complete process without influencing the transport constant. 3. The incorporation of leucine into adipose tissue protein was diminished to 10% by amiloride in a concentration of 3 × 10−4 M. Experiments with [1-14C]-α-aminoisobutyric acid allow the conclusion that the amino acid transport through the membrane of the adipose tissue remains uninfluenced. 4. The effects of amiloride on the adipose tissue are similar to those of triamterene and of 6-aminonicotinamide. In addition, they all inhibit renal sodium and potassium transport in the distal part of the nephron. 5. It is possible, that there is a connection between the inhibiting effects of these drugs on the incorporation of leucine into the protein of adipose tissue and the disturbance of transport processes through biological membranes.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 5 (1969), S. 61-66 
    ISSN: 1432-0428
    Keywords: Insulin ; islets of Langerhans ; mouse ; collagenase ; glucose ; mannoheptulose ; glucagon ; adrenaline ; phentolamine ; theophylline ; tolbutamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé La libération de l'insuline pendant l'incubation des îlots de Langerhans de la souris, isolés après digestion du pancréas par la collagénase, a été étudiée, et l'influence de divers facteurs sur la vitesse de libération a été recherchée. Le glucose à 3.0 mg/ml (glucose élevé) stimulait la libération d'insuline, mais n'avait pas d'effet à 0.6 mg/ml (taux bas). Le mannoheptulose bloquait la stimulation provoquée par du glucose élevé, comme le faisait l'adrénaline. L'effet de l'adrénaline était aboli par la phentolamine, un agent bloquant alpha adrénergique. Le glucagon seul, ainsi qu'en pre'sence d'un taux de glucose bas, stimulait la libération d'insuline, mais non de façon constante avec un taux de glucose élevé. L'adrénaline abolissait la stimulation provoquée par le glucagon. La théophylline stimulait la libération lorsque le glucose était bas, mais beaucoup moins lorsque le glucose était élevé et pas du tout avec le glucagon, quelle que soit la concentration de glucose. Le tolbutamide stimulait la libération d'insuline avec une faible concentration de glucose et cet effet n'était pas inhibé par l'adrénaline. La convenance de cette préparation pour des études sur le métabolisme des cellules insulaires et sa relation avec la sécrét ion d'insuline est discutée.
    Abstract: Zusammenfassung Es wurde die Insulinausschüttung aus Langerhans'schen Inseln von Mäusen, die durch Kollagenase-Behandlung des Pankreas gewonnen worden waren, untersucht und der Einfluß verschiedener Faktoren auf die Freisetzungsgeschwindigkeit überprüft. Eine hohe Glucose-Konzentration von 3.0 mg/ml förderte die Insulin-Ausschüttung, während die niedrige Konzentration von 0.6 mg/ml keine Wirkung ergab. Mannoheptulose und Adrenalin blockierten die Stimulation durch die hohe Glucosekonzentration. Der AdrenalinEffekt konnte durch Phentolamin, eine alpha-Rezeptoren blockierende Substanz, wieder aufgehoben werden. Glucagon führte allein und in Gegenwart der niedrigen Glucosekonzentration zu einer verstärkten Insulininkretion: dies war jedoch bei Kombination mit der hohen Glucosekonzentration nicht konstant der Fall. Adrenalin hob die Stimulierung durch Glucagon auf. Theophyllin führte bei Gegenwart der niedrigen Glucosekonzentration zu einer gesteigerten Ausschüttung, dieser Effekt trat unter der höheren Glucosekonzentration in wesentlich geringerem Umfang und bei Zusatz von Glucagon und einer der beiden verwandten Glucosekonzentrationen überhaupt nicht auf. Bei niedriger Glucosekonzentration stimulierte Tolbutamid die Insulinfreisetzung; dieser Effekt ließ sich durch Adrenalin nicht aufheben. Die Aussagefähigkeit dieses Präparates für Untersuchungen des Inselzell-Stoffwechsels und seiner Beziehungen zur Insulininkretion wird diskutiert.
    Notes: Summary The release of insulin during incubation of mouse islets of Langerhans, isolated after digestion of the pancreas with collagenase, has been studied, and the influence of various factors on the rate of release investigated. Glucose at 3.0 mg/ml (high glucose) stimulated insulin release, but had no effect at 0.6 mg/ml (low glucose). Mannoheptulose blocked the stimulation by high glucose, as did adrenaline. The adrenaline effect was abolished by phentolamine, an alpha-adrenergic blocking agent. Glucagon alone, stimulated insulin release, and also with low glucose, but not consistently with high glucose. Adrenaline abolished the stimulation by glucagon. Theophylline stimulated release with low glucose, much less so with high glucose and not at all with glucagon at either glucose concentration. Tolbutamide stimulated release with low glucose, and this effect was not inhibited by adrenaline. The suitability of this preparation for studies of islet cell metabolism and its relationship to secretion of insulin is discussed.
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  • 8
    ISSN: 1432-0428
    Keywords: Insulin ; 32P incorporation ; adenine nucleotides ; guanine nucleotides ; Na+K+ ATP-ase ; ouabain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Le but de ces investigations a été de contribuer à la compréhension du mécanisme d'action de l'insuline, en provoquant un turn-over accru du phosphate inorganique marqué au32P, en ATP et autres mononucléotides, dans le diaphragme du rat. Pendant l'incubation du diaphragme intact de rat dans un milieu bicarbonaté de Krebs Ringer, sans addition de substrat, on n'a pas observé d'effet de l'insuline sur le contenu en adénine-nucléotides, en guanine-nucléotides, y compris le 3′5′ AMP cyclique et le 3′5′ GMP cyclique. Quand du phosphate inorganique radioactif marqué au32P était présent dans le milieu, l'insuline augmentait l'activité spécifique du phosphate inorganique intracellulaire et provoquait une incorporation accrue du32P dans l'ATP et le GTP. L'effet sur l'ADP était moins prononcé. Il a été montré que ces effets de l'insuline dépendent de la composition ionique du milieu et du transport membranaire des ions. L'augmentation due à l'insuline de l'activité spécifique du phosphate inorganique intracellulaire et du marquage accru au32P de l'ATP (et du GTP) était en grande partie inhibée par l'ouabaïne. Pendant l'incubation dans les milieux où le chlorure de sodium a été remplacé isoosmotiquement par le chlorure de potassium ou de choline, les effets de l'insuline décrits ci-dessus étaient abolis. Les résultats indiquent que le marquage accru de l'ATP (et du GTP) provoqué par l'insuline, peut être en premier lieu attribué à des phénomènes survenant au niveau de la membrane cellulaire. L'augmentation de l'activité spécifique du phosphate inorganique intracellulaire en présence d'insuline, peut s'expliquer par une captation accrue du phosphate inorganique marqué au32P, à partir du milieu. Apparemment le marquage accru au32P de l'ATP (et du GTP) est une conséquence secondaire. On suggère que cet effet de l'insuline est d'abord en rapport avec un effet sur les enzymes de la membrane, en particulier sur l'ATP-ase activée par Na+, K+ et Mg2+.
    Abstract: Zusammenfassung Ziel dieser Untersuchungen war es, zu einem besseren Verständnis der stimulierenden Wirkung von Insulin auf den Einbau von anorganischem32P Phosphat in ATP und andere Mononucleotide im Rattenzwerchfell beizutragen. Während der Inkubation intakter Rattenzwerchfelle in Krebs-Ringer-Bicarbonat Puffer ohne Substratzusatz konnte kein Insulineffekt auf den Gehalt an Adenonucleotiden und Guaninnucleotiden, sowie von cyclischem 3′,5′ AMP und cyclischem 3′,5′ GMP beobachtet werden. In Gegenwart von anorganischem32P Phosphat steigerte Insulin die spezifische Aktivität von intrazellulärem anorganischen Phosphat und bewirkte einen verstärkten Einbau von32P in ATP und GTP. Die Wirkung auf ADP war weniger ausgeprägt. Es konnte gezeigt werden, daß diese Insulineffekte von dem IonenGehalt des Mediums und dem Membrantransport der Ionen abhängen. Die Steigerung der spezifischen Aktivität des anorganischen Phosphates und der Markierung von ATP (und GTP) mit32P ließ sich weitgehend durch Ouabain wieder aufheben. Bei Inkubation in Pufferlösungen, die statt NaCl isoosmolare Mengen von KCl oder Cholinchlorid enthielten, waren die oben erwähnten Insulineffekte nicht mehr nachweisbar. Die Resultate sprechen dafür, daß die verstärkte Markierung von ATP (und GTP) unter Insulin in erster Linie auf Vorgängen an der Zellmembran beruht. Die erhöhte spezifische Aktivität des intrazellulären anorganischen Phosphates in Gegenwart von Insulin läßt sich durch einen verstärkten Einstrom von32P Phosphat aus dem Medium erklären. Augenscheinlich kommt es dadurch sekundär zu einer gesteigerten32P Markierung von ATP (und GTP). Wir möchten annehmen, daß dieser Insulineffekt vorwiegend über die Membranenzyme erfolgt und sich vor allem auf die Na+, K+ und Mg++ aktivierbare ATPase erstreckt.
    Notes: Summary The aim of these investigations has been to contribute to an understanding of the mechanism of action of insulin in promoting increased turn over of32P inorganic phosphate into ATP and other mononucleotides in the rat diaphragm. During incubation of the intact rat diaphragm in Krebs Ringer bicarbonate medium without addition of substrate, no effect of insulin on the content of adenine nucleotides and guanine nucleotides including cyclic 3′,5′ AMP and cyclic 3′,5′ GMP has been observed. When32P radioactive inorganic phosphate was present in the medium, insulin increased the specific activity of intracellular inorganic phosphate and promoted an increased incorporation of32P into ATP and GTP. The effect on ADP was less pronounced. It has been shown that these effects of insulin depend upon the ionic composition of the medium and on ion membrane-transport. The insulin-promoted increase of specific activity of intracellular inorganic phosphate and of increased32P labelling of ATP (and GTP) was to a great extent inhibited by ouabain. During incubation in media where sodium chloride had been iso-osmotically replaced by potassium chloride or choline chloride, the above mentioned effects by insulin were abolished. The results indicate that the increased labelling of ATP (and GTP) promoted by insulin can be primarily attributed to events occuring at the cell membrane. The increased specific activity of intracellular inorganic phosphate in the presence of insulin can be explained by increased uptake of32P inorganic phosphate from the medium. Apparently the increased32P labelling of ATP (and GTP) occur as a secondary consequence. It is suggested that this insulin effect is primarily concerned with an effect on membrane enzymes, particularly the Na+, K+, Mg2+ activated ATP-ase.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 5 (1969), S. 304-308 
    ISSN: 1432-0428
    Keywords: Insulin ; bile ; rabbit ; 125I-insulin ; glucose ; galactose ; fructose ; tolbutamide ; phenformin ; liver
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé On trouve de l'insuline immunoréactive dans la bile hépatique de lapins normaux. Moins de 1% d'une dose injectée d'insuline bovine atteint la bile. Quand de l'insuline bovine 125I, seule ou liée à l'anticorps, est administrée par voie intraveineuse, seulement 40% de la radioactivité retrouvée dans la bile est précipitable avec l'acide trichloracétique et moins de 10% réagit avec le sérum anti-insuline de cobaye. Le glucose, le fructose le galactose, le tolbutamide et la phenformine provoquent tous une élévation de l'insuline dans la bile, qui atteint son maximum 40 à 50 min après l'injection. L'alloxane atténue ou abolie ces réponses.
    Abstract: Zusammenfassung Immunoreaktives Insulin wird in der Leber-Galle normaler Kaninchen gefunden. Weniger als 1% einer injizierten Dosis von Rinder-Insulin erreicht die Galle. Wenn man reines oder an Antikörper gebundenes 125I-Rinderinsulin intravenös verabreicht, lassen sich mit Hilfe von Trichloressigsäure nur 40% der Radioaktivität ausfällen, die in der Galle gefunden wird, und weniger als 10% reagieren mit Meerschweinchen-Anti-Insulinserum. Glucose, Fructose, Galaktose, Tolbutamide und Phenformin verursachen ein Ansteigen von Insulin in der Galle, welches ein Maximum innerhalb von 40 bis 50 Min. nach der Injektion erreicht. Alloxan vermindert oder hebt diese Effekte auf.
    Notes: Summary Immuno-reactive insulin is found in the hepatic bile of normal rabbits. Less than 1% of an injected dose of bovine insulin reached the bile. When 125I-bovine insulin alone or complexed with antibody was given intravenously, only 40% of the radioactivity recovered in the bile was precipitable with trichloracetic acid, and less than 10% reacted with guinea pig anti-insulin serum. Glucose, fructose, galactose, tolbutamide and phenformin all caused an elevation in bile insulin, which reached a maximum 40 to 50 min after the injection. Alloxan attenuated or abolished these responses.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 5 (1969), S. 325-330 
    ISSN: 1432-0428
    Keywords: Insulin ; proinsulin ; blood sugar ; mice ; rats ; pancreatectomy ; nephrectomy ; hepatectomy (partial) alloxan diabetes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Chez les rats et les souris le taux du sucre sanguin est abaissé par une proinsuline obtenue à partir de l'insuline bovine (Schmidt et Arens [6]). Chez les rats alimentés et les souris à jeun, le rapport d'activité proinsuline: insuline est de 1∶4, chez les rats à jeun de 1∶2, dans le cas de dose équimolaire et en mesurant l'abaissement maximum du sucre sanguin. L'abaissement du sucre sanguin évolue de façon plus lente après proinsuline qu'après insuline. La proinsuline, incubée in vitro avec la trypsine, agit quantitativement et au point de vue temps, comme l'insuline. Chez les rats pancréatectomisés, chez les rats néphrectomisés ainsi que chez ceux hépatectomisés aux deux tiers, l'action de la proinsuline est la même que chez les animaux normaux. Les souris rendues diabétiques par l'alloxane répondent également à la proinsuline comme les souris intactes. L'action hypoglycémiante de la proinsuline se manifeste de façon retardée probablement parce que l'insuline active doit tout d'abord se former par un processus protéolytique dépendant du facteur temps. Ceci pourrait être aussi la raison pour laquelle, Rubenstein et coll. [5] signalent l'absence d'effet de la proinsuline dans le test de convulsion chez la souris.
    Abstract: Zusammenfassung An Ratten und Mäusen wird der Blutzucker durch ein aus Rinderinsulin gewonnenes Proinsulin (Schmidt und Arens [6]) gesenkt. Bei gefütterten Ratten und nüchternen Mäusen ist das WirkungsVerhältnis Proinsulin: Insulin = 1∶4, bei nüchternen Ratten 1∶2, wenn äquiznolar dosiert und das Maximum der Blutzuckersenkung gewertet wird. Die Blutzuckersenkung verläuft nach Proinsulin protrahierter als nach Insulin. Proinsulin, welches in vitro mit Trypsin inkubiert wurde, wirkt quantitativ und zeitlich wie Insulin. Bei pankreatektomierten, bei nephrektomierten und bei zweidrittelhepatektomierten Ratten wirkt Proinsulin ebenso wie an Normaltieren. Auch alloxandidbetische Mäuse sprechen auf Proinsulin wie intakte Mäuse an. Die hypoglykämische Wirkung des Proinsulins tritt wahrscheinlich deshalb verzögert ein, weil das aktive Insulin in einem zeitabhängigen proteolytischen Prozeß erst entstehen muß. Dies könnte auch die Ursache für eine von Rubenstein et al. [5] zitierte, fehlende Wirkung von Proinsulin im Mäusekrampftest sein.
    Notes: Summary Proinsulin obtained from bovine insulin (Schmidt and Arens [6]) lowered the blood sugar level of rats and mice. The activity ratio proinsulin: insulin was 1∶4 in fed rats and fasted mice, and 1∶2 in fasted rats, based on an equimolar dosage and measuring the effect in terms of maximum lowering of the blood sugar value. After proinsulin the decrease of the blood sugar was more protracted than after insulin. Proinsulin which was incubated with trypsin in vitro, resembled insulin in degree and onset of action. In pancreatectomized, nephrectomized and two-thirds hepatectomized rats proinsulin acted as in normal animals. Alloxan-diabetic mice responded to proinsulin like intact mice. The reason why the onset of the hypoglycaemic action of proinsulin was delayed is probably due to the fact that the active insulin must first be produced by a time-dependent proteolytic process. This may also be the cause of the ineffectiveness of proinsulin in the mouse convulsion test which was quoted by Rubenstein et al. [5].
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  • 11
    ISSN: 1432-0428
    Keywords: Insulin ; mouse tissues ; kidney fluorescence microscopy ; microscopy ; autoradiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé La localisation d'insuline marquée avec I125 ou avec de l'isothiocyanate de fluorescéine a été étudiée au moyen d'autohistoradiographie au microscope optique, au microscope électronique et au moyen de microscopie à fluorescence dans les tissus de souris à jeun et de souris alimentées normalement. L'hormone fluorescente a été trouvée dans les cellules des tubules proximaux du rein de souris à jeun seulement, tandis que l'hormone radioactive a été repérée aussi dans le rein de souris alimentées, bien qu'en quantité inférieure à celle trouvée chez les souris à jeun. Au microscope électronique la radioactivité est présente dans le rein dans la bordure en brosse, les vacuoles et les mitochondries apicales et le noyau, mais pas dans l'appareil de Golgi ou dans les lysosomes. —L'hormone radioactive est aussi présente dans les autres tissus mais sans différence quantitative entre les souris à jeun et les souris alimentées. Les auteurs concluent que le procédé de ré-absorption de l'insuline par les cellules des tubules proximaux du rein est spécifique: l'hormone n'est pas dégradée de la même façon que les autres protéines mais probablement stockée afin de contrôler les processus métaboliques relevant des organelles subcellulaires dans lesquelles elle se trouve.
    Abstract: Zusammenfassung Gefütterte und fastende Mäuse erhielten fluoreszierendes oder mit125J markiertes Insulin i.v. Die Lokalisation des Insulins in den Geweben wurde untersucht. Nur bei Tieren im Hungerzustand fand sich das fluoreszierende Hormon in den Nieren, während sich das radioaktive Insulin bei gefütterten und fastenden Tieren in den proximalen Tubulusschlingen der Nieren nachweisen ließ. Die fastenden Tiere schienen dabei mehr Radioaktivität aufzuweisen. Wurden die Nieren unter Verwendung von Techniken mit hohem Auflösungsvermögen untersucht, so fand sich die Radioaktivität im Bürstensaum, in den apikalen Vakuolen und Mitochondrien und dem Kern, jedoch nicht im Golgi-Apparat oder den Lysosomen. Alle anderen Gewebe enthielten Hormon-Radioaktivität, aber weder ihre Menge noch ihre Lokalisation unterschieden sich bei gefütterten und fastenden Tieren. Es wird gefolgert, daß der Prozeß der Insulinabsorption durch die Zellen der proximalen Tubulusschlingen spezifisch ist und daß das Hormon nicht in ähnlicher Weise wie andere Eiweißkörper abgebaut wird. Wahrscheinlich kommt es über eine Speicherung zu einer Steuerung der entsprechenden Stoffwechselprozesse in den subzellulären Organellen, in denen das Hormon sich befindet.
    Notes: Summary Starved and fed mice were injected intravenously with either fluorescent or125I-insulin and the localization of the hormone was investigated in various tissues. The fluorescent hormone was found in the kidney of starved animals only, whereas the radioactive hormone was found in the proximal convoluted tubule cells of the kidney of both fed and fasted animals, although the latter group appeared to contain more radioactivity than the first. With high resolution techniques the radioactivity in the kidney was found in the brush border, the apical vacuoles, the apical mitochondria and the nucleus, and never in the Golgi apparatus or the lysosomes. All other tissues contained radioactivity due to the hormone, but no difference in either the amount or the localization was found between fed an starved animals. It is concluded that the process of absorption of insulin by the cells of the proximal convoluted tubules is specific and that the hormone is not degraded in a way similar to other proteins, but is likely to be stored and to control cellular metabolic processes from its sites of localization.
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  • 12
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    Diabetologia 5 (1969), S. 195-197 
    ISSN: 1432-0428
    Keywords: Insulin ; glucagon ; adipose tissue ; lipolysis ; FFA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé A des concentrations proches de celles qui sont rencontrées dans le plasma humain, le glucagon stimule fortement la lipolyse au niveau de la graisse épididymaire du rat, étudiéein vitro. Les effets de telles concentrations de glucagon sont réduits, voire abolis par l'insuline aux concentrations de 25 et 100μU/ml. Rapprochées de l'effet insulinogénique puissant du glucagon, ces observations peuvent fournir une explication quant au caractère retardé de l'élévation du taux sanguin des acides gras libres observée après injection de glucagonin vivo.
    Abstract: Zusammenfassung Glucagon stimuliert in Konzentrationen, wie sie auch im menschlichen Plasma vorkommen, die Lipolyse im Ratten-Nebenhodenfettgewebein vitro stark. Die Effekte derartiger Glucagonkonzentrationen werden durch Insulin (25–100μE/ml) verringert bis aufgehoben. Unter Berücksichtigung der ausgeprägten Wirkung von Glucagon auf die Insulinfreisetzung können diese Beobachtungen eine Erklärung für die Verzögerung des Anstiegs der freien Fettsäuren im Serum liefern, die man nach Glucagoninjektionenin vivo beobachtet.
    Notes: Summary Glucagon in concentrations similar to those found in human plasma markedly stimulates lipolysis in rat adipose tissuein vitro. The effects of these “physiological” concentrations of glucagon are reduced or abolished by insulin at concentrations of 25 and 100μU/ml. Considering the marked insulinogenic effect of glucagon these observations may provide an explanation for the delayed increase of blood FFA observed after glucagon injectionin vivo.
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  • 13
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    Diabetologia 5 (1969), S. 143-145 
    ISSN: 1432-0428
    Keywords: Insulin ; galactose ; galactokinase ; deficiency
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Chez deux adultes souffrant d'une déficience en galactokinase la charge orale de galactose a été suivie d'une hypergalactosémie prolongée sans aucune élevation de l'insuline immunoréactive plasmatique.
    Abstract: Zusammenfassung Orale Belastung mit Galactose führte bei zwei Erwachsenen mit Galactokinasemangel zu einer prolongierten Hypergalactosämie, aber nicht zu einem Anstieg des immunoreaktiven Insulins im Plasma.
    Notes: Summary Oral galactose loading in two galactokinase-deficient adults produced the expected high and prolonged rise of galactose in peripheral blood, but no rise of circulating immunoreactive insulin.
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  • 14
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    Psychopharmacology 14 (1969), S. 62-73 
    ISSN: 1432-2072
    Keywords: Amphetamine ; Hallucinogens ; Drug Addiction ; Psychopharmacology ; Phenylethylamines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The amphetamine analog, 2,5-dimethoxy-4-methylamphetamine (DOM), was studied in 18 volunteer subjects given single doses ranging from 2 to 14 mg. The former was a threshold dose, with definite psychotomimetic effects being evident from doses over 5 mg. The clinical syndrome greatly resembled that of the LSD-mescaline-psilocybin series of drugs, including its time-course. Somewhat more sedation was produced by DOM than would have been expected from the others, despite concomitant evidence of peripheral sympathetic stimulation. Just as with the other drugs, DOM increased plasma free fatty acids, decreased phosphorus and creatinine clearance, decreased circulating eosinophils and had little effect on catecholamine excretion. Performance of psychometric tests was impaired. Chlorpromazine treatment concurrently was found to attenuate the reaction. Tolerance rapidly developed when the drug was used chronically by patients.
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  • 15
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    Psychopharmacology 15 (1969), S. 196-206 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Animal Behavior ; Alcohol ; Atropine ; Discrimination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Two operant procedures were used for training albino rats to make differential responses on the basis of their drug or nondrug condition. In the Conflict procedure, every fifth lever press was rewarded by a food pellet in one condition (drug for half the animals, saline for the other half) and was punished by electric shock in the other condition. For 6 animals the drug condition was ethyl alcohol (1200 mg/kg of a 10% v/v solution in isotonic saline, injected i.p. 5 min before the start of the session); for 4 animals the drug condition was atropine sulfate (10 mg/kg in 1 ml/kg saline injected i.p. 30 min before the start of the session). In the Choice procedure, food reward was obtained by the first press on one of two levers at a variable time interval, averaging one minute, after the prior food reward. The rewarded lever depended on the animal's drug or saline condition (alcohol for 7 animals, atropine for 5 animals, administered as in the Conflict procedure); the same right-hand or left left-hand lever was rewarded in the drug condition for half the animals and in the saline condition for the other half. The response associated with 1200 mg/kg alcohol was generally elicited in tests with sufficiently high doses of pentobarbital sodium (10–20 mg/kg), chlordiazepoxide hydrochloride (10–15 mg/kg) and chloral hydrate (90–120 mg/kg, administered orally). Lower doses of these compounds, and of alcohol, were perceived as less similar to the alcohol and therefore more similar to the saline condition. Substantial doses of chlorpromazine hydrochloride (2 mg/kg) and d-amphetamine sulfate (1 mg/kg) also were perceived as similar to the saline condition. The response associated with a centrally acting anticholinergic (10 mg/kg atropine) was generally elicited in tests with several doses of scopolamine hydrobromide (0.06 to 1.0 mg/kg) and of atropine (2.5–5.0 mg/kg). The saline response was elicited by a lower dose of scopolamine (0.03 mg/kg) and by a peripherally-acting anticholinergic, atropine methyl bromide, at a dose (5 mg/kg) equimolar with 10 mg/kg atropine sulfate. The same results, including closely similar ED50 doses, were generally found with the Conflict and Choice procedures, despite the differences between them in the motivational basis for the differential drug and nondrug responses. The similarities and dissimilarities among these compounds in perceived stimulus characteristics also correspond closely with those reported by Overton (1966) with a locomotor shock-escape procedure in tests which were generally limited to a single high dose of each drug.
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  • 16
    ISSN: 1432-2072
    Keywords: Nicotine ; Antimuscarinic Drugs ; Ganglion-Blocking Drugs ; Operant Conditioning ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effects of nicotine on bar-pressing behaviour in the rat are blocked by mecamylamine. The depressant phase of the effect is blocked by atropine, supporting the conclusion that this depression is mediated by released acetylcholine. The quaternary compounds chlorisondamine and atropine methylnitrate also antagonise the behavioural effects of nicotine but the doses required for this are far in excess of those which are effective peripherally, suggesting that the sites of interaction are central.
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  • 17
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    Psychopharmacology 15 (1969), S. 351-360 
    ISSN: 1432-2072
    Keywords: Nicotine ; Conditioned Stimulus ; Discrimination Learning ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Rats were trained to respond for water rewards on different bars in a Skinner box depending on whether they had previously been injected with nicotine or with saline. No other drug tested could consistently elicit responses on the “nicotine correct” bar. Pre-treatment with mecamylamine abolished the rats' ability to distinguish between nicotine and saline but pretreatment with chlorisondamine did not.
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  • 18
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    Psychopharmacology 14 (1969), S. 142-149 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Amphetamine ; Cholinergics ; Drug Interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Amphetamine was administered to a group of rats trained on a nondiscriminated avoidance procedure. An intraperitoneal dose of 2.0 mg/kg caused about a 75% increase in response rate for the three-hour session. Doses of atropine, Tremorine, eserine, and 4-(1-naphthylvinyl)-pyridine (NVP), an inhibitor of the enzyme choline acetylase, which were ineffective in themselves, markedly affected the increase in rate observed after amphetamine. The quarternary amine of NVP was without effect on the amphetamine response. Those agents that decreased cholinergic function, either by blocking the effect of acetylcholine or by preventing its synthesis, augmented the stimulating effect of amphetamine. Cholinergic stimulants, on the other hand, significantly antagonized the behavioral effects of amphetamine.
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  • 19
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    Psychopharmacology 14 (1969), S. 221-232 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Animal Behaviour ; Nicotine ; Punishment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effects of nicotine, amphetamine, chlordiazepoxide and caffeine were studied in rats trained on a VI 2 crf schedule of water reward with all rewards accompanied by electric shock. Responding, partially suppressed by the shock, was restored by chlordiazepoxide and further suppressed by amphetamine. Nicotine resembled amphetamine in its effects on most rats but occasionally increased responding. Caffeine also increased responding in some rats indicating that this property is not always confined to tranquillising drugs.
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  • 20
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    Psychopharmacology 14 (1969), S. 200-210 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Hashish ; Cannabinoids ; Monkeys Amphetamine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. The psychopharmacological activity of Δ 1-tetrahydrocannabinol, (I); Δ 1(6)-tetrahydrocannabinol (4′ hexyl), (II); Δ 1(6)-tetrahydrocannabinol, (III); 1-ethoxyhexahydrocannabinol, (IV); 8-ethoxy-iso-hexahydrocannabinol, (V); Δ 1(6)-tetrahydrocannabinolic acid Me ester, Isomer I, (VI); Δ 1(6)-tetrahydrocannabinolic acid Me ester, Isomer II, (VII); cannabigerol, (VIII); Δ 1(6)-tetrahydrocannabinol (3′ hexyl), (IX); cannabichromene, (X); has been examined in a variety of animal species. 2. Compounds (I) and (III) caused severe motor disturbances and a stuporous state in dogs and ptosis, “tameness” and peculiar postural changes in monkeys. In the latter animal, compound (II) elicited similar effects. 3. Compounds (I) and (III) after intraperitoneal but not subcutaneous administration, suppressed the gerbil digging activity; reduced the rat conditioned avoidance response and induced a cataleptoid reaction in mice, rats and gerbils. In addition, compound (I) reduced the performance of mice on the rotating-rod. Both compounds, administered subcutaneously, induced a measurable ataxic gait in rats. 4. Amphetamine reversed the behavioural changes elicited by compounds (I) and (III) in monkeys, as well as the cataleptoid reaction in rats. 5. None of the other compounds provoked observable changes in any of the species studied. 6. It is suggested that Rhesus monkeys might serve as a suitable model for assessing the psychopharmacological activity of active cannabinoids.
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  • 21
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    Psychopharmacology 15 (1969), S. 245-254 
    ISSN: 1432-2072
    Keywords: Aggression ; Lithium ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The influence of lithium on aggressive behavior was studied in Siamese fighting fish, mice and golden hamsters. The fish stopped fighting when exposed to concentrations of 10 to 30 meq/l LiCl in the surrounding water. Also in mice and hamsters which ingested LiCl with the drinking fluid lithium abolished intraspecific aggression. Measurements of plasma and brain lithium levels revealed astonishing individual differences in the concentrations which were necessary for the antiaggressive effect. In all species normal aggressive behavior reappeared after lithium treatment was discontinued.
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  • 22
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Antidepressants ; Reserpine Emesis ; Apomorphine Pecking
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Seven psychic energizers have been quantitatively evaluated for their antidepressant and tranquillizing activity using antagonism of reserpine induced emesis and apomorphine induced pecking in pigeons as test procedures for the two activities respectively. Pheniprazine and deanol possess anti-reserpine activity only whereas imipramine, desmethylimipramine, amitriptyline, opipramol and orphenadrine possess both anti-reserpine as well as anti-apomorphine activity. It is suggested that the two tests form a simple and reliable combination for evaluating potential antidepressants.
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  • 23
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    Psychopharmacology 15 (1969), S. 425-429 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Methysergide ; Mania ; Lithium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Six manic patients were studied in an open sequential drug trial of placebo and the serotonin antagonist methysergide; lithium was then substituted double-blind. No dramatic change occurred in individual manic item scores or in mean daily mania ratings after 48 hours or seven days of methysergide, although several of the patients showed slight trends toward improvement. However, after a mean duration of 10.3 days of lithium treatment, all manic item scores improved dramatically and significantly, so that complete clinical remission was evident in all patients. In view of the discrepancy between these essentially negative findings and several recent positive reports on the efficacy of methysergide in the treatment of mania, the authors feel that the indolealkylamine hypothesis of affective disorders should be further investigated.
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  • 24
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    Psychopharmacology 15 (1969), S. 19-27 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Animal Behavior ; Nicotine-Physical Performance ; Motivation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In sessions of ten runs each, swimming time of rats through a 4 m long water alley was measured. Four doses of nicotine (0.05; 0.1; 0.2; 0.4 mg/kg given intraperitoneally 30 minutes before testing) were tested in sessions with a braking load on the tails of the animals either in all 10 runs of a session, or in every second run, or in none of the 10 runs. Regardless of the swimming condition, nicotine produced a considerable, and at doses of 0.1 mg/kg and over, significant decrease of performance in the first two runs. From the third to the 10th run, the changes caused by nicotine were smaller and differed depending on the swimming conditions. A dose of 0.1 mg nicotine/kg improved performance in the “without-load-sessions” and the “without-load-runs” of the alternating sessions, while both 0.1 and 0.2 mg/kg improved performance of the “with-load-runs” of the alternating sessions. Performance in the “without-load-sessions” and the “without-load-runs” was depressed by 0.4 mg/kg and that in the “with-load-sessions” by 0.2 and 0.4 mg/kg.
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  • 25
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    Psychopharmacology 15 (1969), S. 28-38 
    ISSN: 1432-2072
    Keywords: Drugs ; Sleep ; Electroencephalography ; Psychophysiology ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Sleep physiological patterns were examined following a single oral dose (500 mg) of the hypnotic drug alpha chloralose. The drug increased SW sleep and decreased REM sleep without affecting total sleep time or the amount of stage 2. These changes were accompanied by a shift to slower frequencies and greater EEG synchrony, as well as a decrease in the number of spontaneous arousals in all stages of sleep, and throughout the night of medication. Except for a slight decrease in eye movement density, the drug had no systematic effects on phasic phenomena such as electrodermal or cardio-respiratory fluctuations, nor was there a systematic change in basal heart and breathing rates. On the night following medication a “rebound” increase in percent stage REM was associated with a sharp decrease in SW sleep, and increases in spontaneous arousals and waking time. Such findings suggest that sleep stages are controlled by homeostatic mechanisms whose function is to maintain equilibrium. A comparison of the effects of alpha chloralose with those of the barbiturate secobarbital revealed some striking differences. Although both alpha chloralose and the barbiturate reduced the amount of stage REM and the frequency of brief arousals, the latter compound enhanced EEG fast activity and desynchrony, and suppressed such phasic phenomena as rapid eye movements during stage REM, sigma spindles in stage 2, nonspecific electrodermal responses during SW sleep and cardio-respiratory variability in all sleep stages. For secobarbital, the decrease in percent stage REM was compensated by an increase in stage 2 rather than SW sleep. Several studies in the cat suggest that in subanesthetic doses, alpha chloralose acts primarily on cortical inhibitory processes, causing release of the reticular activating system from inhibitory influences. The results of this study show that moderate doses in man probably act on both cortical and subcortical systems involved in the mediation of SW sleep, REM sleep and arousal.
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  • 26
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    Psychopharmacology 15 (1969), S. 134-143 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Anti-Anxiety ; Controlled Trial ; Doxepin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Six patients with persistent anxiety symptoms were used in a preliminary assessment of a new anti-anxiety compound-Doxepin (Sinequan) with placebo. The factorial design is discussed as a potentially useful way of conducting a first-stage test of anti-anxiety compounds. Analysis of the results showed that Doxepin at 25 mg t.d.s. and 50 mg t.d.s. was associated with improvement in the patient's self ratings of anxiety symptoms.
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  • 27
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    Psychopharmacology 15 (1969), S. 144-152 
    ISSN: 1432-2072
    Keywords: Niacin ; Nicotinamide Adenine Dinucleotide ; Schizophrenia ; Phenothiazines ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Two grams of NAD were administered orally to ten chronic schizophrenic patients for twenty-one days. Five of the patients were also receiving thioridazine. There was no gross clinical improvement noted in any of the patients despite the fact that related experiments suggested that the NAD was absorbed. In those patients who were not also receiving phenothiazines there was a distinct tendency towards increased hostility, aggressiveness and irritability beginning one week after the initiation of NAD treatment and lasting for nearly two weeks after the NAD was discontinued.
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  • 28
    ISSN: 1432-2072
    Keywords: Lysergic Acid Diethylamide or LSD ; Methylphenidate or Ritalin ; Chlordiazepoxide or Librium ; Psychopharmacology ; Alcoholism and Drug Therapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Through the retrospective use of the 156 item DWM Card Sort, the experiences from a single intravenous dose of 200 mcg of LSD, 75 mg of methylphenidate (Ritalin) and 75 mg of chlordiazepoxide (Librium) were compared in a population of 99 chronic male alcoholics treated in an “LSD setting” in a double-blind study. Surprisingly, 96 of the 156 items proved significantly different among the 3 groups. LSD was unique in producing Sensory and Perceptual Distortions (including Hallucinations or Illusions), and Mystical, Religious or Paranormal Sensations. However, contrary to expectation, LSD did not uniquely produce the traditional “therapeutic” experience, but appeared to be surpassed in that area by methylphenidate. Both drugs also produced some anxiety, while chlordiazepoxide produced relaxation, and enhanced music appreciation.
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  • 29
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    Psychopharmacology 14 (1969), S. 18-22 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Animal Behaviour ; Mice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Mice were stained with pulverized charcoal and the resulting grooming behaviour observed. From 119 controls, the typical patterns indicated a late cleaning of the tail, the sacrum and the region between the ears. The following substances were tested: Imipramine, Desipramine, Trimeprimine, Amitriptyline, Nortriptyline, Chlordiazepoxide, Iproniazide, d-Amphetamine, Chlorpromazine, Haloperidol, Acetylsalicylic acid, Metronidazole. Of these Amitriptyline, Chlorpromazine, Haloperidol and Metronidazole were effective in doses less than 1/10 of LD 5.
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  • 30
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    Psychopharmacology 14 (1969), S. 248-254 
    ISSN: 1432-2072
    Keywords: Amphetamine ; Appetite Depressants ; Psychopharmacology ; Sympathomimetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A method is described with which it is possible to measure locomotor activity and food intake simultaneously in the same rat or other small animal. From a study of a number of psychomotorstimulant drugs and anorectic agents it may be concluded that locomotorstimulation and appetite-suppression are two different effects that may or may not characterize the same drug. Methamphetamine and phenmetrazine are stimulants in doses that do not inhibit food intake. Amphepramon reduced food intake in low doses but acts as a stimulant in higher doses. Chlorphemternine and phenfluramine are anorectic agents that are not stimulants, even in high doses.
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  • 31
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    Psychopharmacology 14 (1969), S. 394-403 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Morphine ; Skin Conductance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Skin conductance changes during periods of stress induced by hypercapnia were studied during a cycle of addiction to morphine. Conductance changes were found to be dose dependent in both tolerant and non-tolerant states. The effects of morphine on skin conductance changes induced by hypercapnia were similar to those effects previously observed on changes induced by electric shock.
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  • 32
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    Psychopharmacology 14 (1969), S. 417-425 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Psychoses ; Reflex, Abnormal ; Chlorpromazine ; Trifluopromazine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary According to our results in 117 subjects, recently taken medications, age and sex must be considered when duration of the Achilles-tendon reflex is used as a clinical test to assess thyroid status. Males have a shorter ATR than females. In older subjects the ATR lasts longer than in those below age 27. Fifty-two psychiatric patients before medication did not differ in ATR duration from 65 controls. However, after 28 patients took chlorpromazine and 24 received trifluoperazine, ATR was prolonged in the chlorpromazine group and shortened in the trifluoperazine group. Neither chlorpromazine concentrate, 1,800 mg, nor trifluoperazine concentrate, 180 mg, given during the first six days, affected ATR, but an additional 6,000 mg of chlorpromazine, or an additional 420 mg of trifluoperazine over the next six days, did significantly alter ATR-duration.
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  • 33
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Doxepin ; Diazepam ; Anti-Anxiety ; Antidepressant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Doxepin and diazepam were evaluated for therapeutic effectiveness in a double blind study carried out with 69 primarily anxious neurotic outpatients attending either a municipal hospital clinic or a general practitioner's office. Doxepin produced more clinical improvement than diazepam in several questionnaire clusters measuring depressive symptomatology, but not in clusters measuring anxious symptomatology. According to several outcome criteria, doxepin tended to produce more clinical improvement in general practice than in clinic patients, while diazepam produced either equal improvement in both populations or slightly more improvement in the clinic. Possibly contributing to the present results are low daily dosage of diazepam, differential pharmacological drug effects, population differences in levels of anxiety and depression, and differences in population characteristics, primarily as related to social class.
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  • 34
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    Psychopharmacology 15 (1969), S. 1-8 
    ISSN: 1432-2072
    Keywords: Cannabis (Marihuana) ; Lysergic Acid Diethylamide ; Hallucinogens (Psychopharmacology) ; Visual Perception ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Four pigeons were trained on a visual discrimination task which required conditional responding along the independent dimensions of form and color. High doses of Cannabis sativa (marihuana) extract and lysergic acid diethylamide (LSD), which were equated on the basis of their effectiveness in suppressing responding, increased responding on a color dimension but not on a form dimension. High doses of LSD produced a decrement in discrimination performance while comparable doses of Cannabis did not effect accuracy. Treatment with Bromolysergic acid diethylamide, saline, and pentobarbital did not produce significant changes in performance. Results are discussed in terms of a break-down in stimulus control and central hallucinogenic activity.
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  • 35
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    Psychopharmacology 15 (1969), S. 64-72 
    ISSN: 1432-2072
    Keywords: Amphetamine ; Dextro Amphetamine ; Psychopharmacology ; Conditioning, Operant ; Pharmacodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Bar pressing was maintained by food reinforcement of each fiftieth response (FR50 schedule). Rats were tested at 3 levels of food deprivation (60, 80 and 100% of ad libitum body weight) under three drug conditions (0, 0.2 and 0.4 mg of D-amphetamine per rat). Overall response rate was reduced by increasing doses of drug, but not significantly by deprivation, within the range studied. The components of response rate were analysed separately into the starting speed (latency of the first response of each ratio run of 50 responses) and running rate. Drug level affected running rate and first latency of the session, whereas body weight affected only first latency of the session. Only the first latency of the session showed an interaction of drug level and body weight. The lack of interaction raises the question, whether amphetamine is more properly administered as total dose per rat, rather than proportional to body weight.
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  • 36
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    Psychopharmacology 15 (1969), S. 109-115 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Hallucinogens ; Drug Effects ; Behavior Exploratory ; Monkeys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effect of Psilocybin on the behavior of the baboon Papiopapio has been studied. Animal watchfulness, as estimated from the E.E.G., is enhanced within the first five minutes after injection and then is not further modified. Psilocybin induces a decrease of spontaneous motility. Conversely, the frequency of eye movements is considerably increased. This pattern might be explained by alterations of visual perception.
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  • 37
    ISSN: 1432-2013
    Keywords: Toad Bladder ; Sodium Transport Pool ; Aldosterone ; Insulin ; Vasopressin ; Krötenblase ; Natrium-Transport-Pool ; Aldosteron ; Insulin ; Vasopressin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The size of toad bladder sodium transport pool, defined as that amount of sodium of apical origin and recovered in tissue at equilibrium, was compared with sodium transport rate, derived from short-circuit current read immediately before tissue analysis. Provided certain precautions be taken, the relationship between both variables can be described by a curve starting at the intersect ofX (pool, in μEq) andY (transport, in μEq/hr) axes, with a tendency forX to increase faster thanY. Assuming sodium transport pool forms one compartment, its calculated half-life averages 2–3 min. sodium transport pool measurements are thought to shed light on mechanism of sodium transport by toad bladder because pool size was large with respect to transport rate when tissue was exposed to several inhibitors of sodium transport. Conversely, upon stimulation of activity of (substrate — depleted) preparations by glucose, a relative reduction of pool size was observed. Aldosterone, vasopressin (and adenosine 3′,5′-phosphate) increased sodium pool size and transport rate, proportionately; insulin stimulated sodium transport more than it increased pool size. Thus, insulin presumably exerts its effect at the sodium “pump” while such a site of action need not be postulated for aldosterone and vasopressin: these 2 hormones would instead induce, permeability changes faciliting sodium movement at the apical border of toad bladder epithelial cells.
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  • 38
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    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 39
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    International Journal of Chemical Kinetics 1 (1969), S. 1-1 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 40
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    International Journal of Chemical Kinetics 1 (1969), S. 3-9 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C—Cl and C—C bond energies in the chloroethanes and C—H, C—Cl, and C—C bond energies in the chloroethyl radicals are calculated from known heats of formation of chloroethanes and chloroethylenes and known C—H bond energies in chloroethanes.The results obtained show a dependence of bond energy on the isomeric structure of the molecules and radicals and on the type of bond broken (primary, secondary, or tertiary). Heats of formation and bond energies estimated from group property additivity rules are in close agreement with experimental values.
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  • 41
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    International Journal of Chemical Kinetics 1 (1969), S. 11-27 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the pressure dependence of the C5 products from the reaction of cis-butene-2 and methylene is reported. Methylene was produced by the photolysis of diazomethane with 4358 Å light at 23° or 56°, and by photolysis of ketene with 3200 Å radiation at 23° or 100°. The change with increasing pressure of the relative amounts of the characteristically “triplet products” (trans-1,2-dimethylcyclopropane, trans-pentene-2 (TP2), and 3-methylbutene-1 (3MB1)) and “singlet products” (cis-1,2-dimethylcyclopropane (CDMC) and cis-pentene-2 (CP2)) are discussed. The behavior is reminiscent of that found in 3CH2-cis-butene-2 systems and can be interpreted in terms of the rapid rate of rearrangement of an initial triplet diradical product component, due to 3CH2, relative to the slower rate and readier collisional stabilization of an initial vibrationally-excited dimethyl cyclopropane product component, due to 1CH2. Relative rates of reactions of 1CH2 with allylic CH:vinyl CH:C=C in the neat liquid were, for diazomethane, 1:1.1:7.2 and, for ketene, 1:1.2:6.7.
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  • 42
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of iodine monochloride (ICl) as a thermal source of chlorine atoms in known concentration is discussed with particular reference to the suppression, by large excesses of iodine, of the chain processes normally associated with chlorine atom reactions. The kinetics and mechanism of the reaction of ICl with hydrogen are presented in a study covering the temperature range 205-337°C, and the pressure ranges: ICl, 6-20 torr; I2, 3-13 torr; and H2, 9-520 torr. The reaction, followed spectrophotometrically in a static system, is shown to be homogeneous, first order in ICl and in H2, and inverse half-order in I2, over several half-lifetimes of the ICl, yielding HCl as the sole product. The rate data obtained in this work for the reaction are combined with the critically evaluated results of other workers in an Arrhenius plot covering the temperature range 286-730°C, and three orders-of-magnitude in the rate constant, yielding the results, log k1/(1/mole sec) = 10.68-5.26/θ, where θ = 2.303RT in kcal/mole. This value of k1 is lower by a factor of about two than that proposed in a recent review by Fettis and Knox, and is clearly at variance by a factor of two or more with the most recent data of Clyne and Stedman.
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  • 43
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature-jump method has been used to determine the nickel(II)- and cobalt(II)-arginine complexation kinetics. In the pH range studied, the neutral form of the ligand, HL, is the attacking, as well as the complexed, ligand species. The reactions reported on are of the type where n = 1, 2, 3 and M is Ni or Co. At 25° and ionic strength 0.1M the association rate constants are: for nickel(II) k1 = 2.3 × 103(±20%), k2 = 2.4 × 104(±20%), k3 = 3.5 × 104(±40%) M-1 sec-1; for cobalt(II) k1 = 1.5 × 105(±20%), k2 = 8.7 × 105(±20%), k3 = 2.0 × 105(±40%) M-1 sec-1. Arginine binds to metal ions less well than homologous chelating agents due to the electrostatic repulsion arising from the positively charged terminus of the zwitterion. Kinetically, the effect appears in the association rate constants with nickel reactions more strongly influenced than cobalt.
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  • 44
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectrophotometric determination of the rate of iodine atom catalyzed geometrical isomerization of diiodoethylene in the gas phase from 502.8 to 609.1°K leads to a rate constant for the bimolecular reaction between I and trans-diiodoethylene of log kt-c(M-1 sec-1) = 8.85 ± 0.12 - (11.01 ± 0.30)/θ. Estimates of the entropy and enthalpy change for the addition of I atoms to trans-diiodoethylene (process a.b) lead to log Ka.b(M-1) = -2.99 - 4.0/θ, and thus to log kc (sec-1) = log kt-c - log Kab = 11.8 -7.0/θ for the rate constant for rotation about the single bond in the adduct radical. The theory for calculation of the rotation rate constant is presented and it is shown that while the exact value depends on the barrier height, a value of 6.8 kcal/mole for this quantity leads to log k (sec-1) = 11.8 -6.7/θ. The activation energy points to a better value of the group contribution to heat of formation of the group C-(I)2(H)(C) than one based on bond additivity.
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  • 45
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    International Journal of Chemical Kinetics 1 (1969), S. 69-87 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reactions have been investigated in a fast flow system at pressures of about 2 torr and temperatures between 12 and 132°C. The following Arrhenius equations are derived for reaction (2) where the units of k2 are l/mole sec and of E2, cal/mole, and the limits are the 95% confidence limits assuming random errors.These equations are in good agreement with those which can be derived from previous investigations.
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  • 46
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    International Journal of Chemical Kinetics 1 (1969), S. 105-111 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between carbon monoxide and atomic oxygen was studied in a gas flow over a temperature range of 136 to 230°C at atmospheric pressure. The rate constant of this reaction, considered to be one for a second-order reaction, was found to decrease with increasing temperature and to depend on the ratio of O2 to CO that was varied from 0.11 to 2.69. A conclusion was made that under the experimental conditions the reaction was third order The rate constant of this reaction was determined for a mixture of O2 and CO and it was found that the efficiency of O2 as particle M is four times that of CO.
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  • 47
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    International Journal of Chemical Kinetics 1 (1969), S. 113-126 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of solvolysis of benzyl chloride and of substituted benzyl chlorides have been measured in an acetone-water mixture (acetone mole fraction 0.147) at pressures ranging from atmospheric to 1 kbar. Pressure studies have also been made for p-methyl benzyl chloride in various acetone-water mixtures. Measurements have also been made of the partial molar volumes of the reactants. The plots of log k against pressure are fitted to a second-degree polynomial in P, and values of ΔV
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  • 48
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of molecular-modulation spectrometry for studying photochemical reactions has been applied to methyl nitrite photolysis. The infrared absorption of the nitroxyl radical HNO has been observed in the gas phase at 3300 cm-1. Under the present experimental conditions the steady-state concentration of HNO under steady illumination was 1.1 × 1012 particles/cc, and the observed modulation amplitude was 4.5 × 1010 particles/cc. At 25°C and 1 atm of nitrogen, the cross section for infrared absorption by HNO at 3300 cm-1 is 1.7 × 10-19 cm2. The rate constant ratio b/c was found to be 8.0. From the literature value of the rate constant d , the observed rate constant for the reaction is e = (5 ± 1) × 10-11 cc/particle sec.
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  • 49
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    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 50
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectrophotometric determination of the rate of pyrolysis of 1,2-diiodoethylene from 305.8 to 435.0° (with additional data on the addition of iodine to acetylene from 198.1 to 331.6°) has resulted in the observation of both a (in part heterogeneous) unimolecular process (A), and an iodine atom catalyzed process (B). For the homogeneous unimolecular process, log (kA/sec-1) ≈ 12.5-46/θ would appear to be reasonable, while log (kB/M-1 sec-1) = 11.8-23.9/θ, where θ = 2.303RT in kcal/mole.It is suggested that a donor-acceptor complex intermediate may explain the observed rate constant of process B and analogous reactions in other systems.
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  • 51
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    International Journal of Chemical Kinetics 1 (1969), S. 133-146 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal isomerization of the title compounds was studied in the vapor phase. Over the temperature range from 445.1 to 477.5°K, 1,4-dimethylbicyclo[2.2.0]hexane underwent a homogeneous unimolecular reaction to 2,5-dimethyl-1,5-hexadiene, the rate constants being represented by the equation: k = 1.86 × 1011 exp (-31000 ± 1800/RT) sec-1. Over the temperature range from 630.0 to 662.2°K, 1,4-dimethylbicyclo[2.1.1]-hexane also underwent a unimolecular isomerization to the same product, the rate constants being given by the equation: k = 8.91 × 1014 exp (-56000 ± 900/RT) sec-1. The pyrolysis of 1,4-dimethylbicyclo[2.1.0]pentane gave 1,3-dimethylcyclopentene-1 and 2,4-dimethyl-1,4-pentadiene in the ratio of 9:1. The former reaction was influenced by surface effects but the latter was not. The rate constants for the formation of 2,4-dimethyl-1,4-pentadiene fitted the equation: k = 1.66 × 1017 exp (-57400 ± 3100/RT) sec-1. The effect of the two methyl groups at the bridgehead positions in these molecules in influencing the rate of decomposition is discussed in terms of the non-bonded repulsive forces between the substituents.
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  • 52
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    International Journal of Chemical Kinetics 1 (1969), S. 157-170 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isotope effects, general acid catalysis, and relative reactivities show that proton transfer to one of the unsaturated carbon atoms is rate determining for the acidolysis of unsaturated alkylmercuric halides. For compounds, R1R2C=CHHgX, substitution of CH3 for H at R1 or R2 leads to an acceleration of a factor of ∼ 30. This relatively small acceleration, the relative facility of the reactions, and the magnitude of the Br- catalytic terms, suggests an olefin-mercuric halide complex as the product of the rate-determining step, rather than a simple carbonium ion.The Brøonsted catalysis law is obeyed with a variety of carboxylic acids, giving an ∝ of 0.69 ± 0.04, but acids of other structures give substantially deviant catalytic coefficients, in a pattern similar to that generated by other A-SE2 reactions. The acetic acid catalytic coefficient is larger by a factor of 102 than that predicted if it were due to specific hydronium ion-general base catalysis instead of true general acid catalysis.The overall solvent isotope effect, kH/kD, is 2.55 ± 0.10. The competitive isotope effect, κH/κD, is 6.84 ± 0.06. Taken with a model in which the proton is transferred directly from the H3O+ unit of the aquated proton to the substrate, these are sufficient to successfully predict the rate at all intermediate isotopic compositions.
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  • 53
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    International Journal of Chemical Kinetics 1 (1969), S. 171-191 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of azomethane-d6 has been studied. There is a short chain reaction, and measurements have been made of the rate of production of N2, CD4, and C2D6. A mechanism is suggested which accounts for these results fairly well. A comparison is made with some similar results of Forst for azomethane. Measurements have also been made of the reaction inhibited by NO. It is believed that the N2 production, extrapolated to zero NO pressure, measures the rate of the initial step CD3N2CD3 → 2 CD3 + N2. This has an activation energy at high pressures of 50.7 kcal per mole and an Arrhenius A·factor of 1015.49 sec-1. This is to be compared to values of 55.5 and 1017.3 found by Forst and Rice for CH3N2CH3 → 2 CH3 + N2. The pressure fall-off behavior for CD3N2CD3 → 2 CD3 + N2 has also been investigated and compared to the theoretical curves, which seem to fit satisfactorily except at the lowest pressure, where experimental errors may be large. Unexpectedly, the fall-off curve crosses that for CH3N2CH3 → 2 CH3 + N2. It is suggested that the extrapolation to zero NO pressure may not be entirely correct in the CH3N2CH3 case where the chain is longer than with CD3N2CD3. It is believed that the decomposition of azomethane-d6 is a better example for unimolecular-rate theory than is that of azomethane.
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  • 54
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    International Journal of Chemical Kinetics 1 (1969), S. 193-207 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: t-Butylperoxy α-phenylisobutyrate (I) decomposes thermally by concerted formation of carbon dioxide, t-butoxy, and cumyl radicals. Radical pair return in the solvent cage therefore does not affect the observed rate of decomposition, but is readily determined by means of galvinoxyl and other scavengers. In a series of 15 solvents the rate constant varies over a 2.8 fold range, being fastest in aromatic solvents. In the same solvent series the relative rates of diffusion and combination of radicals, measured by the cage effect, change by tenfold and are largely determined by the viscosity of the solvent. In all solvents of η 〉 8 mP, the reciprocal of the cage effect is a linear function of (T1/2/η), as recently observed for trifluoromethyl and methyl radicals [16]. This property of the cage effect provides a test by which it can be distinguished from other processes that reduce the efficiency of free-radical production from an initiator.
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  • 55
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    International Journal of Chemical Kinetics 1 (1969), S. 279-282 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 56
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of ozonation of C2H4 and C2H2 have been studied in the gas phase from -40 to -95°C (C2H4) and +10 to -30°C (C2H2). The O3 concentrations were near 10-4 M, and the hydrocarbons were present in 2- to 25-fold excess. A few experiments with propylene were also carried out. The reactions were followed by observing the rate of decay of O3 absorption at 2537 Å. Reaction stoichiometries and effects of added O2 were investigated. The second-order rate constant for C2H4 was log k(M-1 sec-1) = (6.3 ± 0.2) - (4.7 ± 0.2)/θ (θ = 2.3RT). The rate was independent of the presence of excess O2. Rate measurements for C3H6 were less accurate because of aerosol interference. Combined with room temperature measurements of other workers, the C3H6 rate constant was log k(M-1 sec-1) = (6.0 ± 0.4) - (3.2 ± 0.6)/θ. The C2H2 rate constant was log k(M-1 sec-1) = (9.5 ± 0.4) - (10.8 ± 0.4)/θ. In the case of C3H6 the major product was propylene ozonide. Ethylene did not yield the ozonide, and the products of the O3-C2H4 and O3-C2H2 reactions were not identified. Pre-exponential factors for the olefin reactions are consistent with a five-membered ring transition state formed by 1,3 dipolar cycloaddition of O3. For C2H2, however, the much higher observed A factor suggests a different mechanism. Possible transition states for the O3-C2H2 reaction are discussed.
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  • 57
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    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 58
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods are presented for rapidly estimating the entropies and heat capacities of free radicals from the known S0 and Cp0 of structurally similar compounds. The methods consist of estimating the differences due to changes in mass, vibration frequencies, spin, symmetry, and changes in rotational barriers. Tables of contributions to S0 and Cp0 by different frequencies over the temperature range 300-1500°K are presented to facilitate the tabulation of the above differences. Conjugated radicals, such as benzyl and allyl, are included. It is shown that the greatest uncertainties in the estimates arise from uncertainties in the barriers to rotation in the radicals.The results are applied to kinetic data on the pyrolysis of branched hydrocarbons and the reverse reactions of radical recombination. Major discrepancies exist in these data which can be nearly reconciled by postulating improbably high rotational barriers of 8 kcal for CH3 rotation in isopropyl and t-butyl radicals.It is shown that radical thermochemistry can be fitted into group schemes and tables of groups values are given for the rapid estimation of ΔHf0, S0, and Cp0 for different organic radicals, including those containing sulfur, oxygen, and nitrogen.
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  • 59
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the reaction CH2I2 + HI ⇆ CH3I + I2 has been followed spectrophotometrically from 201.0 to 311.2°. The rate constant for the reaction fits the equation, log (k1/M-1 sec-1) = 11.45 ± 0.18 - (15.11 ± 0.44)/θ. This value, combined with the assumption that E2 = 0 ± 1 kcal/mole, leads to ΔHf298° (CH2I, g) = 55.0 ± 1.6 kcal/mole and DH298° (H—CH2I) = 103.8 ± 1.6 kcal/mole.The kinetics of the disproportionation, 2 CH3I ⇆ CH4 + CH2I2 were studied at 331° and are compatible with the above values.
    Additional Material: 6 Ill.
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  • 60
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several hydrocarbons have been pyrolyzed in a single pulse shock tube. Rate parameters for the main bond breaking step have been found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm iC}_3 {\rm H}_7 {-\!-} {\rm CH}\left({{\rm CH}_3} \right){\rm CH} {\raise1pt\hbox{$\Relbar \kern-4pt{\Relbar}$}} {\rm CH}_2 \longrightarrow {\rm iC}_3 {\rm H}_7 \cdot + \cdot {\rm CH}\left({{\rm CH}_3} \right){\rm CH} {\raise1pt\hbox{$\Relbar \kern-4pt{\Relbar}$}} {\rm CH}_2} \right\} = 10^{15.70} \exp \left({{{- 32,500} \mathord{\left/ {\vphantom {{- 32,500} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm iC}_3 {\rm H}_7 {-\!-} {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5 \longrightarrow {\rm iC}_3 {\rm H}_7 \cdot + \cdot {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5} \right\} = 10^{16.15} \exp \left({{{- 35,900} \mathord{\left/ {\vphantom {{- 35,900} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm C}_2 {\rm H}_5 {-\!-} {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5 \longrightarrow {\rm C}_2 {\rm H}_5 \cdot + \cdot {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5} \right\} = 10^{16.57} \exp \left({{{- 38,800} \mathord{\left/ {\vphantom {{- 38,800} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm iC}_3 {\rm H}_7 {-\!-} {\rm CH}_2 {\rm C}_6 {\rm H}_5 \longrightarrow {\rm iC}_3 {\rm H}_7 \cdot + \cdot {\rm CH}_2 {\rm C}_6 {\rm H}_5} \right\} = 10^{15.23} \exp \left({{{- 34,800} \mathord{\left/ {\vphantom {{- 34,800} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} In combination with similar studies carried out earlier and through application of the well-established experimental rule (kr2(AB)/kr(AA)kr(BB))1/2 ∼ 2 where A and B are radicals and the rate constants are for the combination of these radicals, rate parameters for the thermal decomposition of all the hydrocarbons formed from any pair of the following radicals: methyl, ethyl, isopropyl, t-butyl, t-amyl, allyl, methylallyl, and benzyl have been calculated. The available calculated and experimental values of the decomposition rate constants are in excellent agreement. It appears that, with the possible exception of reactions involving the ejection of methyl radicals, the frequency factors per bond are nearly constant, depending only upon the type of carbon-carbon bond that is being broken. These values are all lower than those expected from the radical recombination rates.Heats of formation of ethyl, t-amyl, benzyl, methylallyl, n-propyl, s-butyl, isobutyl, neopentyl, and 3-pentyl radicals have been derived.Rate parameters for the decomposition of some simple ketones and ethers have also been estimated.
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  • 61
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the photoinitiated reductions of methyl iodide and carbon tetrachloride by tri-n-butylgermanium hydride in cyclohexane at 25°C have been studied and absolute rate constants have been measured. Rate constants for the combination of CH3ċ and CCl3ċ radicals are equal within experimental error and are also equal to the values found for the self-reactions of most non-polymeric radicals in low viscosity solvents, i.e. ∼1-3 × 109 M-1 sec-1.Rate constants for hydrogen atom abstraction by CH3ċ and CCl3ċ radicals are both ∼1-2 × 105 M-1 sec-1. Tri-n-butyltin hydride is about 10-20 times as good a hydrogen donor to alkyl radicals as is tri-n-butylgermanium hydride.The strength of the germanium-hydrogen bond, D(n-Bu3Ge-H) is estimated to be approximately 84 kcal/mole.
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  • 62
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    International Journal of Chemical Kinetics 1 (1969), S. 353-356 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 63
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    International Journal of Chemical Kinetics 1 (1969), S. 325-337 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermally and radiation initiated chain reaction between trichloroethylene and cyclopentane to produce 1,1-dichlorovinylcyclopentane and hydrogen chloride have been investigated in the temperature range 250-360°C at high pressure in the gas phase. The rate governing step in the chain is (k3 = 3.3 × 109 exp -(4800/RT) cc mole-1 sec -1). The rate of the unimolecular decomposition of trichloroethylene is 1.4 × 1014 exp -(61,200/RT) sec-1.
    Additional Material: 5 Ill.
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  • 64
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    International Journal of Chemical Kinetics 1 (1969), S. 297-314 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase, nitric oxide catalyzed positional isomerization of 3-methylene-1,5,5-trimethylcyclohexene (MTC) into 1,3,5,5-tetramethyl-1,3-cyclohexadiene (TECD) has been studied for temperatures ranging between 296° and 425°C. The major reaction was first order with respect to nitric oxide and to MTC.The major side product, mesitylene, usually amounted to less than 10% of the TECD isomer formed. Only at high temperatures and large conversions has up to 20% been observed.Conditioned pyrex or quartz vessels coated with KCl have been used. The nitric oxide catalyzed isomerization is apparently a homogeneous process, as demonstrated by the insensitivity of the observed rate constants towards a 15-fold increase in the surface to volume ratio of the reaction vessels. However, a residual, presumably heterogeneous, thermal isomerization of the starting material could not be eliminated. Good mass balances were obtained for both NO and hydrocarbons.After correcting for the thermally induced conversion the observed rate constants for the nitric oxide catalyzed isomerization yield log k1 (1 mole-1 sec-1) = (10.7 ± 0.2) - (37.3 ± 0.9)/θ where θ is 2.303 × 10-3 RT (kcal mole-1). Plotting log k1 versus the ratio of the starting materials (MTC/NO)0 it was found that for temperatures ≥ 365°C the rate constants were systematically too high.Using extrapolated values for the higher temperature range yields the more reliable corrected Arrhenius equation log k1corr = 8.6 - 31.7/θ. The reaction mechanism is outlined and the implications with respect to the stabilization energy generated in the MTCċ radical intermediate and the activation energy of the backreaction MTCċ + HNO are discussed.Using for the activation energy E-1 of the backreaction (Rċ + HNO) a literature value of 9.2 ± 0.9 kcal mole-1 reported for the cyclohexadiene—1,3—system, this yields 23.4 ± 2 kcal mole-1 for the stabilization energy in the methylenecyclohexenyl radical, which is to be compared with the corresponding values for the allyl (10.2 ± 1.4), methallyl (12.6 ± 1) pentadienyl (15.4 ± 1) and cyclohexadienyl (24.6 ± 0.7) radicals.The pre-exponential factor agrees well with the value of (8.4 ± 0.2) reported by Shaw and co-workers for the similar reaction of NO with 1,3-cyclohexadiene. It is noteworthy that HNO, acting as sole hydrogen donor in the system, is surprisingly stable under the reaction conditions used. Nitrous oxide, HCN, H2O and N2 are observed in the product mixture of experiments carried out to high conversions at higher temperatures.
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  • 65
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    International Journal of Chemical Kinetics 1 (1969), S. 339-351 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following Arrhenius parameters have been determined for the hydrogen-abstraction reactions: R + (CH3)4Si → RH + (CH3)3SiCH3 TextRTemp. (°K)E (kcal/mole)Log A (mole-1 cc sec-1)Log k(400°K) (mole-1 cc sec-1)CF3330-4337.23 ± 0.0911.90 ± 0.057.95CH3396-47610.23 ± 0.3611.55 ± 0.185.68CD3396-49610.36 ± 0.1211.84 ± 0.066.20C2H5423-52211.40 ± 0.4811.88 ± 0.225.68The activation energies are in keeping with the strengths of the bonds formed during the reaction. By comparison with the activation energies for the analogous reactions of neopentane it is estimated that D((CH3)3SiCH2—H) ≃ 97 kcal/mole.The A factors for the above series of reactions fall within the range predicted by transition-state theory for this type of process and the validity of previous results of Kerr, Slater, and Young is seriously in doubt.
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  • 66
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    International Journal of Chemical Kinetics 1 (1969), S. 357-359 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 67
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    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 68
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    International Journal of Chemical Kinetics 1 (1969), S. 391-399 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of elementary iodine, isobutyl iodide (2-methyl-1-iodopropane) undergoes isotopic exchange and also decomposes with production of additional iodine. Both reactions are approximately first order in isobutyl iodide and half order in iodine molecules. In degassed hexachlorobutadiene at 160°, the rate constants for exchange and decomposition are 7.5 × 10-6 and 11.4 × 10-6 (liter/mole)1/2sec-1, respectively. The decomposition is probably initiated by iodine atom abstraction of a β hydrogen atom, but comparison with rates for related compounds indicates that this hydrogen abstraction does not contribute significantly to the mechanism of exchange.
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  • 69
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of the reaction between iodine and dimethyl ether (DME) have been studied spectrophotometrically from 515-630°K over the pressure ranges, I2 3.8-18.9 torr and DME 39.6-592 torr in a static system. The rate-determining step is, where k1 is given by log (k1/M-1 sec-1) = 11.5 ± 0.3 - 23.2 ± 0.7/θ, with θ = 2.303RT in kcal/mole. The ratio k2/k-1, is given by log (k2/k-1) = -0.05 ± 0.19 + (0.9 ± 0.45)/θ, whence the carbon-hydrogen bond dissociation energy, DH° (H—CH2OCH3) = 93.3 ± 1 kcal/mole. From this, ΔH°f(CH2OCH3) = -2.8 kcal and DH°(CH3—OCH2) = 9.1 kcal/mole.Some nmr and uv spectral features of iodomethyl ether are reported.
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  • 70
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    International Journal of Chemical Kinetics 1 (1969), S. 371-380 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Arrhenius parameters have been determined for the hydrogen-abstraction reactions: R + SiHCl3 + RH + SiCl3 TextRTemp (°K)E(kcal/mole)Log A(mole-1 cc sec-1)Log k(400°K) (mole-1 cc sec-1)CF3323-4615.98 ± 0.0611.77 ± 0.038.50CH3333-4434.30 ± 0.0810.83 ± 0.044.48C2H5314-4135.32 ± 0.0711.54 ± 0.048.63The trend in activation energies ECH3 〈 EC2H5 〈 ECF3 is interpreted as indicating a polar effect in the reaction of CF3 with SiHCl3 and the similar reactivities of all three radicals appear to be due to the high exothermicity of the reactions.The A Factors for the reactions are normal for hydrogen abstraction reactions of free radicals. The previous results of Kerr, Slater, and Young for CH3 abstracting an H atom from SiHCl3 have been amended.
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  • 71
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    International Journal of Chemical Kinetics 1 (1969), S. 361-370 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stable nitroxide radicals and ESR techniques have been used to investigate rotational and translational motions of molecules in the liquid state. It is found that for hydrocarbons and molecules with low polarity the rotational frequencies are about an order of magnitude faster than translational encounters. Arrhenius parameters are reported for the rates of both types of processes. A scheme is given for the relation of these motions to radical recombination in solution and also to reactions requiring activation energy. The consequences of this scheme are examined.Such important properties as hydrodynamic fluidity, thermal conductivity, processes of extraction and solution, occurring in the liquid phase as well as at the interface are determined by mobility of particles in the liquid. The problem of molecular mobility is of essential significance for the kinetics of chemical and chemico-physical processes in the liquid phase.Application of both ESR techniques and stable nitroxide radicals for kinetic studies of molecular motions in liquids and the correlation between molecular mobility and the kinetic parameters of liquid-phase radical reactions have been studied in the present paper.
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  • 72
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    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 73
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    International Journal of Chemical Kinetics 1 (1969), S. 413-425 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of pentafluoroacetone has been investigated in the 3130 Å region, from room temperature to 360°C. The ΦCO varies from 0.7 to 0.9 over this range, and the decomposition is represented by CF2HCOCF3 → CF2H + CO + CF3. The disproportionation/combination ratio for CF3 and CF2H (→ CF3H + CF2) radicals is found to be 0.09. Arrhenius parameters for hydrogen atom abstraction from the ketone are log10A = 12.7 (units are mole-1 cc sec-1) and E = 14.3 kcal mole-1 for CF2H, and log10A = 12.1 and E = 11.8, for CF3 radicals. At low pressures HF elimination reactions are observed from the vibrationally excited fluoroethanes, C2F5H* and C2F4H2*, formed in the system. A rough estimate of the activation energy for the process C2F5H → C2F4 + HF of 60-65 kcal mole-1 is made.
    Additional Material: 3 Ill.
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  • 74
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The activating effects of a number of unsaturated groups and a cyclopropyl group have been evaluated in a solvent free system by determining the absolute rate constants, and energies and entropies of activation in the vapor phase pyrolysis of secondary and tertiary esters of the type RC(R′CH3) OAc where R′ = H or CH3 and R = c-Pr, i-Pr, CH3, CH2=CH, CH2=CHCH2, C6H5; the cyclopropyl showed only a moderate activating effect. The results are in contrast to the very significant activating effect of a cyclopropyl group in solvolysis of cyclopropylcarbinyl derivatives. Apparently marked activation by this group occurs only when a highly developed positive center forms adjacent to it. The lack of marked activation by the cyclopropyl group supports a mechanism for ester pyrolysis which involves a modest, but detectable, charge separation in the transition state [2] but questions a mechanism in which an intimate ion-pair was proposed [3].
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  • 75
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase reaction I2 + HCOOCH3 → HI + CH3I + CO2 has been studied spectrophotometrically in a static system over the pressure ranges I2 (6-39 torr) and HCOOMe (28-360 torr). In the temperature range 293-356°, the initial rate of disappearance of I2 is first order in [HCOOMe] and half-order in [I2]. The rate determining step is where k1 is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} \left({k_1 /{\rm M}^{- 1} \sec ^{- 1}} \right) = \left({9.6 \pm 0.3} \right) - \left({22.4 \pm 0.8} \right)/\theta $$\end{document} where θ = 2.303 RT in kcal/mole. This activation energy gives a carbonyl C—H bond strength of 92.7 kcal/mole. At 356° there was no evidence of abstraction of a methoxy hydrogen, so a lower limit of 100 kcal/mole may be placed on this C—H bond strength. These ester C—H bond strengths are discussed in relation to comparable values in aldehydes and ethers.
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  • 76
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    International Journal of Chemical Kinetics 1 (1969), S. 439-450 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative rates of addition of difluorocarbene to a series of methyl-substituted olefins have been determined and correlated with similar data for dichlorocarbene, chlorofluorocarbene and ground-state oxygen atoms. The electrophilic nature and stabilization of difluorocarbene by the fluorine substituents is discussed. Relative activation energies for the difluorocyclopropane-forming reaction have been estimated and correlated with properties of the olefins as derived from molecular orbital theory.
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  • 77
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    International Journal of Chemical Kinetics 1 (1969), S. 451-458 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Data on the kinetics of S2F10 pyrolysis, which gives SF4 + SF6, have been reinterpreted to give a value for the equilibrium constant of S2F10 ⇆ SF4 + SF6. This, together with statistical estimates of the entropy and heat capacity of S2F10, can be used to give for this reaction values of ΔH298° = 19.7 ± 1.0 kcal/mole and ΔS300° = 47.6 ± 2 gibbs/mole. ΔHf°(S2F10) = -494 kcal/mole. A compatible mechanism is shown to be S2F10 ⇆ 2SF5 (fast); 2SF5 ⇆ SF6 + SF4 (slow) with step 2 rate-determining. The overall, best first order rate constant is proposed as kmeas = 1017.42-43.0/θ sec-1 = K1k2, where θ = 2.303RT in kcal/mole.Independent measurements of δHf° and S° for the SF5 radical, permits the evaluation of the equilibrium constant K1 = 108.92-(27.1 ± 6)/θ l./mole-sec and yields k2 = 108.50-15.9/θ l./mole-sec. The observed homogeneous catalysis by NO and CHCl = CHCl can be explained in terms of a direct abstraction of F from S2F10 : C + S2F10 → CF + S2F9, followed by S2F9 → SF5 + SF4 and SF5 + CF ⇆ SF6 + C (C ≡ NO or C2H2Cl2).
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  • 78
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    International Journal of Chemical Kinetics 1 (1969), S. 479-481 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 79
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    International Journal of Chemical Kinetics 1 (1969), S. 473-477 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase isomerization of 1,1-dimethyl-2-vinylcyclopropane to cis-2-methylhexa-1,4-diene has been studied in a static system. The isomerization is homogeneous and kinetically first order. The rate constants were independent of initial reactant pressure in the range 0.6 to 2 torr and of added nitrogen up to 180 torr. Rate constants determined at 10 temperatures in the range 200 to 254°C fitted the Arrhenius equation k = 1011.41±0.02 exp (-33,540 ± 47 cal/RT) sec-1The low A factor and activation energy are consistent with a concerted 1,5-hydrogen migration via a “tight” cyclic transition complex.
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  • 80
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    International Journal of Chemical Kinetics 1 (1969), S. 459-472 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The intramolecular elimination of isobutene from 2-d1-triisobutylaluminum has been studied in the gas phase for temperatures ranging between 102.4 and 184.6°C. The reaction is apparently homogeneous and obeys the first order rate law, yielding the following Arrhenius relationship: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \,k_{{\rm el}im} \left( {\sec ^{ - 1} } \right) = 11.1 - {{27.2} \mathord{\left/ {\vphantom {{27.2} {\theta \,{\rm where}\,\theta \,{\rm equals}\,4.58 \times 10^{ - 3} }}} \right. \kern-\nulldelimiterspace} {\theta \,{\rm where}\,\theta \,{\rm equals}\,4.58 \times 10^{ - 3} }}T\left( {{}^ \circ {\rm K}} \right)\,{\rm in}\,{\rm units}\,{\rm of}\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mole}{\rm .}}}} \right. \kern-\nulldelimiterspace} {{\rm mole}{\rm .}}} $$\end{document} Excess ethylene was added to the starting material in order to avoid complications from the backreaction. The cyclic 4-center nature of the transition state proposed earlier has been unequivocally demonstrated by deuterium labelling. Mass-spectral analyses show that the isobutene formed contains no deuterium. The hydrolyses products of the mixed trialkylaluminum formed during the reaction consist of monodeuteroethane and 2-d1-isobutane. The observed negative entropy of activation of ∼12 cal/°-mole agrees with prediction and implies a reasonably tight transition state structure. Combined with the corresponding data for the non deuterized Al(i-bu)3 reported earlier, these data result in a primary kinetic deuterium isotope effect of kH/kD = 1.3 × 100.6/θ corresponding to a ratio of the isotopic rate constants of 3.7 at 25°C. This result is in excellent agreement with a predicted value of 1.4 × 100.7/θ and it is in line with literature data on similar reactions involving cyclic transition state complexes.
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  • 81
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    International Journal of Chemical Kinetics 1 (1969), S. 483-486 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 82
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    International Journal of Chemical Kinetics 1 (1969), S. 487-492 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 83
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    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 84
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    International Journal of Chemical Kinetics 1 (1969), S. 493-494 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 85
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 86
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    International Journal of Chemical Kinetics 1 (1969), S. 499-508 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase bond isomerization of allyl fluoride, allyl chloride and allyl bromide, catalyzed by HBr and ultraviolet light, has been studied in the temperature range of 150-250° and at pressures of 3.5 to 50 mm. The reactions are very clean, first order in allyl halide and HBr, and have a light intensity exponent of unity. A quantum yield for allyl chloride of 3200 indicates a chain reaction. Dilution with inert gases is almost without effect, indicating that excited state intermediates are not involved. A small wall effect is observed. The evidence indicates a free radical reaction, involving hydrogen abstractions by bromine atoms, with replacement at the other end of the allylic radical.
    Additional Material: 4 Ill.
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  • 87
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By photolyzing (CF2H)2CO and (CFH2)2CO the hydrogen atom abstraction reactions of CF2H radicals with (CF2H)2CO, H2, D2, CH4, C2H6, n—C4H10 and iso—C4H10, and the reactions of CFH2 radicals with (CFH2)2CO and n—C4H10, have been studied. Arrhenius parameters for these reactions are compared with related systems. From a knowledge of the activation energies for the forward and reverse reactions a value of the bond dissociation energy, D(CF2H—H) = 97.4 ± 1.3 kcal mole-1 at a mean temperature of 543°K is obtained. This value is subject to much uncertainty due to possible compensation effects in the Arrhenius parameters. These effects are discussed for this and the other reactions, and the data suggest that D(CF2H—H) is approximately 100 kcal mole-1, and that D(CFH2—H) is very similar. Other literature data tend to confirm these approximate values.
    Additional Material: 5 Ill.
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  • 88
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    International Journal of Chemical Kinetics 1 (1969), S. 527-539 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This review presents in tabular and graphical form rate data on the reactions of atomic oxygen (O3P) with methane and ethane. The reliability of these data is discussed and suggested values of the rate constants are given over specified temperature intervals. Specific values are given for 298 and 1000°K.
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  • 89
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    International Journal of Chemical Kinetics 1 (1969), S. 581-583 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 90
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    International Journal of Chemical Kinetics 1 (1969), S. 551-569 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed kinetic model of the HCl chemical laser produced by the flash photolytically initiated H2—Cl2 explosion is described, and the results of computer calculations on such a system are discussed. It is shown that currently accepted values of the various rate constants, supplemented in a few cases by reasonable estimates of previously unmeasured rate constants, are adequate to approximate the observed laser behavior of this system. It is also shown that the chemistry of such a system is extremely complex, and exhibits a high degree of coupling between one reaction and another; therefore, great care is required to extract kinetic data from the optical behavior of such laser systems. It is further argued that different hydrogen halide lasers may behave quite differently from each other, depending on the relative magnitudes of the various rate constants involved.
    Additional Material: 6 Ill.
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  • 91
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    International Journal of Chemical Kinetics 1 (1969), S. 541-549 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal dissociation of COS was investigated in shock waves with argon as carrier gas. The concentration was varied between 0.05 and 0.5% COS in argon, the total density from 2.5 × 10-5 mole/cm3 to 2.5 × 10-3 mole/cm3. Temperatures between 1500°K and 3100°K were applied.For the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm COS}\left({^1 \Sigma} \right)\mathop {\longrightarrow}\limits^{K_{\rm 1}} {\rm CO}\left({^1 \Sigma ^ +} \right) + {\rm S}\left({^3 P} \right) $$\end{document} the rate constant was found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{10} \approx 10^{14.2} \exp - \left({\frac{{61000}}{{RT}}} \right) \quad\quad ({\rm cm}^3 {\rm mole}^{- 1} \sec ^{- 1}) $$\end{document} in the low pressure range of the unimolecular reaction and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1\infty} \approx 10^{11.6} \exp - \left({\frac{{61000}}{{RT}}} \right) \quad\quad (\sec ^{- 1}) $$\end{document} in the high pressure range.
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  • 92
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    International Journal of Chemical Kinetics 1 (1969), S. 571-580 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of methyl radicals to tetrafluoroethylene in the gas phase has been studied over the temperature range 80-180°C, using a material balance method. \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} + {\rm C}_2 {\rm F}_{\rm 4} \to {\rm CH}_3 {\rm C}_2 {\rm F}_4 $$\end{document}Arrhenius parameters of 1011.95±0.23 (mole-1 cm3 sec-1) and 5.7 ± 0.4 (kcal/mole) have been measured for the addition reaction.Electrophilic reagents such as O or CF3 appear to react almost equally readily with ethylene and tetrafluoroethylene but methyl radicals add much more rapidly to tetrafluoroethylene than to ethylene, the difference in reactivity being principally due to an activation energy difference of ∼2 kcal/mole.
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  • 93
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    International Journal of Chemical Kinetics 1 (1969), S. 585-587 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 94
    ISSN: 1432-5233
    Keywords: Bovine insulin ; Insulin ; Insulin antibodies ; Insulin resistance ; Pork insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Les AA. présentent les résultats obtenus avec une méthode très simple pour la recherche des anticorps anti-insuline, basée sur l'emploi d'insuline I125 ou I131 et sur la précipitation avec alcool absolu du complexe antigène-anticorp. Les anticorps anti-insuline ont été fréquemment observés seulement dans des sujets diabétiques déjà soumis à traitement avec insuline. Un taux élevé d'anticorps anti-insuline s'accompagne à une diminution de la sensibilité à l'insuline (0,1 U/kg i.v.).
    Abstract: Resumen Se expresan los resultados obtenidos con el empleo de un método que puede ser ejecutado en forma my simple, para la investigación de anticuerpos anti-insulina; el método se basa sobre el empleo de insulina I125 o I131; y sobre la precipitación sucesiva con alcohol absoluto del complejo antígeno-anticuerpo. Los anticuerpos anti-insulina han sido hallados con mucha frecuencia solamente en pacientes diabéticos, que recibían tratamiento insulínico. Un título elevado de anticuerpos antiinsulina se asocia a una disminución sensible de la sensibilidad a la insulina (0,1 U/kg i.v.).
    Notes: Riassunto Vengono presentati i risultati ottenuti con l'impiego di una metodica di semplice esecuzione per la ricerca di anticorpi anti-insulina, basata sull'impiego di insulina I125 o I131 e sulla successiva precipitazione con alcool assoluto del complesso antigene-anticorpo. Gli anticorpi anti-insulina sono stati riscontrati con grande frequenza solo in pazienti diabetici già sottoposti a trattamento insulinico. Un elevato titolo di anticorpi anti-insulina si associa ad una diminuzione marcata della sensibilità all'insulina (0,1 U/kg i.v.).
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  • 95
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    Acta diabetologica 5 (1968), S. 279-298 
    ISSN: 1432-5233
    Keywords: Choline ; Clinical situation (diabetes) ; Glucagon ; Growth hormone ; Heparin ; Histamine ; Insulin ; Insulinemia ; Night vision ; Pro-insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Alors que mon intérêt pour l'insuline a été pratiquement continu depuis déjà sa découverte, il y a eu des périodes pendant lesquelles mon attention s'est concentrée sur la coline, l'histamine et l'héparine. Pendant les années de guerre, les sujets de recherche ont été naturellement très différents. Les points importants dans le développement de l'insuline, du point de vue chimique, ont été sa purification, cristallisation, détermination de la structure et synthèse. Les physiologistes ont été fascinés par les études regardant le point et le mécanisme d'action de l'insuline. On a appris beaucoup quant à l'action sur grand nombre de tissus différents et l'insuline se montra être la principale hormone anabolique. Les développements cliniques ne sont mentionnés que brièvement car mes intérêts personnels de recherche ont été exclusivement expérimentaux.
    Abstract: Resumen Mientras mi interés para insulina fue prácticamente continuo desde su descubrimiento, hubo períodos en que mi atención se concentró sobre colina, histamina y heparina. Durante los años de la guerra, los temas de investigación fueron naturalmente muy diferentes. Los puntos fundamentales en el desarrollo de la insulina desde el punto de vista químico, fueron su purificación, cristalización, determinación de la estructura y síntesis. Los fisiólogos fueron cautivados por los estudios sobre el punto y el mecanismo de acción de la insulina. Mucho se aprendió acerca de la acción sobre muchos tejidos diferentes y la insulina demostró ser la hormona anabólica principal. Los desarrollos clínicos se mencionan sólo brevemente pues mis intereses personales de investigación han sido exclusivamente experimentales.
    Notes: Riassunto Mentre il mio interesse per l'insulina è stato praticamente continuo sin dalla sua scoperta, ci sono stati periodi nei quali la mia attenzione si concentrò sulla colina, istamina ed eparina. Durante gli anni della guerra, i temi di ricerca furono naturalmente molto diversi. I momenti culminanti nello sviluppo dell'insulina, dal punto di vista chimico, furono la sua purificazione, cristallizzazione, determinazione della struttura e sintesi. I fisiologi sono stati affascinati dagli studi circa il punto ed il meccanismo di azione dell'insulina. Molto è stato appreso intorno all'azione su molti tessuti differenti e l'insulina dimostrò di essere l'ormone anabolico principale. Gli sviluppi clinici sono menzionati solo brevemente poichè i miei personali interessi di ricerca sono stati esclusivamente sperimentali.
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  • 96
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    Acta diabetologica 5 (1968), S. 347-363 
    ISSN: 1432-5233
    Keywords: Diabetes mellitus ; Gel-filtration ; Insulin ; 125J-insulin-plasma complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Les AA. ont étudié la capacité des protéines plasmatiques de lier l'insuline125J avec la méthode de filtration surgel. Le fractionnement parSephadex G-100 a démontré que seulement le 10 % de l'insuline marquée était lié par le protéines plasmatiques des sujets sains, des femmes gravides et des diabétiques non traités. Un pourcentage d'insuline beaucoup plus élevé était liée par les protéines plasmatiques dans des sujets que étaient traités precédemment avec de l'insuline bovine, tandis que le degrée de la liason était tres élevé dans les diabétiques insulino-résistants. De recherches avecSephadex G-200 ont demontré que, après une courte période d'insulinothérapie, le complexe insuline-protéine migrait avec les globulines 19 S. Après une insulinothérapie prolongée et dans les cas insulino-résistants la plus grande partie de l'insuline marquée liée aux protéines était élui avec les globulines 7 S. Le phénomène est attribué à l'action des anticorps anti-insuline bovine.
    Abstract: Resumen La capacidad que poseen las proteínas para ligar la insulina marcada con125J se estudió mediante el método de filtración engel. El fraccionamiento medianteSephadex G-100 demostró que solamente el 10 % de la insulina marcada estaba ligada por las proteínas plasmáticas de sujetos sanos, de mujeres embarazadas y de pacientes diabéticos no tratados. Un porcentaje de insulina notablemente superior estaba ligado por las proteínas plasmáticas en pacientes que anteriormente habían sido tratados con insulina bovina, mientras el grado de enlace se volvía muy elevado en los diabéticos resistentes a la insulina. Experimentos realizados conSephadex G-200 demostraron que después de un breve tratamiento insulínico, el complejo insulina-proteína migraba con las globulinas 19 S. Después de un prolongado tratamiento insulínico y en los casos resistentes a la insulina, la mayor parte de la insulina marcada con las proteínas resultaba eluida con las globulinas 7 S. El fenómeno, discutido detalladamente, se atribuye a la acción de los anticuerpos anti-insulina bovina.
    Notes: Riassunto La capacità delle proteine plasmatiche di legare l'insulina marcata con125J è stata studiata mediante il metodo di filtrazione sugel. Il frazionamento medianteSephadex G-100 ha dimostrato che soltanto il 10% dell'insulina marcata era legato dalle proteine plasmatiche di soggetti sani, di donne gravide e di pazienti diabetici non trattati. Una percentuale di insulina notevolmente superiore era legata dalle proteine plasmatiche in pazienti che erano stati precedentemente trattati con insulina bovina, mentre il grado di legame diveniva molto elevato nei diabetici insulino-resistenti. Esperimenti eseguiti conSephadex G-200 hanno dimostrato che, dopo una breve terapia insulinica, il complesso insulina-proteina migrava con le globuline 19 S. Dopo prolungata terapia insulinica e nei casi insulino-resistenti la maggior parte dell'insulina marcata legata alle proteine era eluita con le globuline 7 S. Il fenomeno, discusso nei particolari, è attribuito all'azione degli anticorpi anti-insulina bovina.
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  • 97
    ISSN: 1432-5233
    Keywords: Insulin ; Insulin antibodies ; Insulin binding properties of serum ; Insulin therapy ; Serum proteins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Les AA. ont observé que le sérum d'un sujet normal et celui d'un diabétique, jamais traité avec insuline, ont la possibilité de lier l'insuline dans la même mesure. Dans certains sérums, soit du sujet normal soit du diabétique, est présente une activité de liaison de l'insuline supérieure aux taux normaux plus élevés; cette activité diminue après administration de µU 500 d'insuline bovine. Les AA. présentent leurs considérations à propos de ce phénomène.
    Abstract: Resumen Los AA. observan que los sueros del individuo normal y del diabético nunca tratado con insulina poseen propiedades insulino-ligantes de entidad análoga. En algunos sueros — ya del sujeto normal, ya del diabético — está presente una actividad insulino-ligante superior a los valores máximos normales, que disminuye luego de haber agregado µU 500 de insulina bovina. Los AA. hacen algunas consideraciones interpretativas de tal fenómeno.
    Notes: Riassunto Gli AA. rilevano che i sieri dell'individuo normale e del diabetico mai trattato con insulina sono provvisti di proprietà insulino-legante di entità analoga. In alcuni sieri, sia del soggetto normale che del diabetico, è presente un'attività insulino-legante superiore ai valori massimi normali, che diminuisce dopo aggiunta di µU 500 di insulina bovina. Gli AA. fanno alcune considerazioni interpretative su tale fenomeno.
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  • 98
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    Acta diabetologica 5 (1968), S. 499-512 
    ISSN: 1432-5233
    Keywords: Entero-insular axis ; Gastrin ; Glucagon ; Gut hormones ; Insulin ; Pancreozymin ; Secretin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Des préparations hautement purifiées de gastrine, sécrétine et pancréozymine ont été injectées par voie endoportale chez des chiens anesthésiés, en vue d'examiner les influences possibles des hormones gastro-intestinales sur la sécrétion des îlots de Langerhans. On a vu que les trois hormones provoquent une augmentation immédiate de la concentration d'insuline dans la veine pancréatico-duodénale. L'effet de la gastrine sur la libération d'insuline était insignificant quantitativement, tandis que celui de la sécrétine était plus important et de plus grande durée; cependant la pancréozymine semblait être le stimulant le plus puissant et déterminer en outre une augmentation parallèle de la sécrétion pancréatique de glucagon. On a démontré de plus que la pancréozymine augmentait la réponse tant de l'insuline que du glucagon à l'hyperaminoacidémie. On a observé que l'administration intraduodénale d'acides aminés, qui représente notoirement la stimulation la plus puissante de la pancréozymine endogène, est en mesure de déterminer une libération plus grande et plus rapide d'insuline et de glucagon par rapport à l'administration intraveineuse d'acides aminés, ce qui fait supposer que la pancréozymine endogène joue un rôle physiologique lorsque la réponse de l'hormone des cellules insulaires aux acides aminés ingérés est augmentée. Le facteur physiologique qui augmente la réponse insulaire au glucose ingéré reste toutefois inconnu.
    Abstract: Resumen Medicamentos altamente purificados de gastrina, secretina y pancreozimina han sido inyectados por via intraportal a perros anestesiados, con el fin de examinar las posibles influencias de las hormonas gastro-intestinales sobre la secreción de las hormonas de las islas de Langerhans. Se ha notado que las tres hormonas producen aumento inmediato de la concentración de insulina en la vena pancreática-duodenal. El efecto de la gastrina sobre la liberación de insulina era insignificante cuantitativamente, mientras el de la secretina era apreciable y de mayor duración; sin embargo, parecía que la pancreozimina fuese el estimulante más potente y que además determinava aumento paralelo de la secreción pancreática de glucagón. Además se ha demostrado que la pancreozimina aumentava la respuesta, ya de la insulina, ya del glucagón, a la hiperaminoacidemia. La administración intraduodenal de aminoácidos, que representa notoriamente el más potente estímulo de la pancreozimina endógena, está en grado de provocar una liberación mayor y más rápida de insulina y glucagón, que la administración intravenosa de aminoácidos; cosa que hace pensar que la pancreozimina endógena ejerce un papel fisiológico cuando aumenta la respuesta de la hormona de las células de las islas a los aminoácidos ingeridos. Sin embargo, el factor fisiológico que aumenta la respuesta insular a la glucosa ingerida, queda desconocido.
    Notes: Riassunto Preparati altamente purificati di gastrina, secretina e pancreozimina sono stati iniettati per via endoportale in cani anestetizzati, allo scopo di esaminare le possibili influenze degli ormoni gastro-intestinali sulla secrezione degli ormoni delle isole di Langerhans. Si è riscontrato che tutti e tre gli ormoni provocano un immediato aumento della concentrazione di insulina nella vena pancreatico-duodenale. L'effetto della gastrina sulla liberazione di insulina era quantitativamente insignificante, mentre quello della secretina era più rilevante e di maggiore durata; tuttavia sembrava che la pancreozimina fosse il più potente stimolatore e che inoltre determinasse un aumento parallelo della secrezione pancreatica di glucagone. Per di più si è dimostrato che la pancreozimina aumentava la risposta sia dell'insulina che del glucagone alla iperaminoacidemia. La somministrazione intraduodenale di aminoacidi, che rappresenta notoriamente la più potente stimolazione della pancreozimina endogena, è stata riscontrata in grado di determinare una liberazione maggiore e più rapida di insulina e di glucagone rispetto alla somministrazione endovenosa di aminoacidi, il che fa pensare che la pancreozimina endogena svolga un ruolo fisiologico nell'aumentare la risposta dell'ormone delle cellule insulari agli aminoacidi ingeriti. Tuttavia il fattore fisiologico che aumenta la risposta insulare al glucosio ingerito rimane sconosciuto.
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  • 99
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    Naunyn-Schmiedeberg's archives of pharmacology 260 (1968), S. 254-268 
    ISSN: 1432-1912
    Keywords: Bilirubin ; Glucuronates ; Insulin ; Liver ; Tolbutamide ; Bilirubin ; Glucuronidsynthese ; Insulin ; Leber ; Tolbutamid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Lebergewebe von Ratten, die mit Tolbutamid, mit anderen blutzuckerwirksamen Sulfonylharnstoffderivaten oder mit Insulin behandelt worden waren, bildet bei Inkubation in vitro mehr Bilirubinglucuronid als das Gewebe unbehandelter Kontrolltiere. Dieser Effekt wurde 2 Std nach der intraperitonealen Injektion der blutzuckersenkenden Stoffe nachgewiesen, er tritt dosisabhängig auf und ist mit der blutzuckersenkenden Wirkung gut korreliert. Ein dem Tolbutamid chemisch verwandtes, jedoch blutzuckerunwirksames Methylsulfonylharnstoffderivat hatte diese Wirkung nicht. Die Steigerung der Glucuronidsynthese ist dadurch bedingt, daß in der Leberzelle während einer Insulin- oder Sulfonylharnstoffhypoglykämie vermehrt aktivierte Glucuronsäure (UDPGA) für die Konjugation bereitgestellt wird. Die Aktivität des für die Konjugationsreaktion verantwortlichen Enzyms, der UDP-Glucuronyltransferase, war unter unseren Versuchsbedingungen nicht verändert. Es fanden sich keine Anhaltspunkte dafür, daß in der Insulin- oder Sulfonylharnstoffhypoglykämie die Bildung von UDPGA aus UDPG beschleunigt erfolgt. Die Aktivität der UDPG-Dehydrogenase war nicht verändert, auch Faktoren, die eine Bildung von UDPGA begünstigen könnten, wie ein erhöhter NAD+/NADH-Quotient und eine gesteigerte ATP-Konzentration im Gewebe, waren nach Tolbutamid nicht nachzuweisen.
    Notes: Summary Liver tissue of rats pretreated with tolbutamide, with other hypoglycaemic sulfonylurea compounds, or with insulin formed more bilirubinglucuronide when incubated in vitro than the tissue of untreated controls. The effect was present two hours after the blood sugar lowering agents had been injected intraperitoneally. It was dose-dependent and well correlated to the hypoglycaemic response. A methylated sulfonylurea compound, which is chemically closely related to tolbutamide but devoid of blood sugar lowering activity failed to show this effect. Glucuronide formation in hypoglycaemia induced by insulin or tolbutamide is increased as more activated glucuronic acid (UDPGA) is made available to the conjugation reaction. There was no change in the activity of the enzyme responsible for glucuronide synthesis, the UDP-glucuronyl-transferase, in our experiments. There was no indication that the formation of UDPGA from UDPG was accelerated by insulin or sulfonylureas. There was no change in the activity of the hepatic UDPG-dehydrogenase. Factors which could favour the formation of UDPGA such as an increased NAD+/NADH ratio or an elevated ATP concentration in the tissue were not present following tolbutamide.
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  • 100
    ISSN: 1432-0428
    Keywords: Insulin ; 3′,5′-AMP phosphodiesterase ; glycogen metabolism ; lipolysis ; insulin secretion ; antilipolytic action of insulin ; glycogen synthesis and insulin ; cyclic adenosine 3′,5′-monophosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé L'influence de l'insuline sur le métabolisme du glycogène hépatique et sur la lipolyse semble s'exercer par l'intermédiaire d'une diminution de la concentration de 3,′5′-AMP intracellulaire. Onamontré une diminution de la formation de 3′5′-AMP dans le tissu adipeux incubé avec de l'insuline. L'influence de l'insuline sur la dégradation du 3,′5′-AMP est étudiée. — L'activité de la 3,′5′-AMP-phos-phodiestérase (PDE) est diminuée dans le foie, le tissu adipeux et, de façon non-significative, dans le muscle strié des rats qui manquent d'insuline, c-à-d les rats rendus diabétiques par l'alloxane ou les rats privés de nourriture. L'injection intraveineuse d'une faible dose d'insuline (0.5 U/kg) ou la stimulation de la sécrétion d'insuline endogène par une injection de glucose provoquent une augmentation rapide de l'activité de la phosphodiestérase dans ces tissus. 15 min après l'injection d'insuline, l'activité de la phosphodiesterase du foie est augmentée. L'effet maximum est atteint après 30–45 min. L'activité de la phosphodiestérase rénale n'est pas diminuée dans le diabète alloxanique, l'injection d'insuline s'est avérée inefficace.In vitro, l'insuline cristalline a un effet activant sur la phosphodiestérase purifiée du coeur de boeuf. La concentration d'insuline requise pour doubler l'activité de l'enzyme est de l'ordre de 2 · 10−5 M. Le traitement avec actinomycin D empêche la stimulation par l'insuline de la PDE dans le foie. Ceci peut indiquer que l'action de l'insuline sur l'activité de la phosphodiestérase est essentiellement basée sur une synthèse accrue de l'enzyme. A cause de l'influence de la sécrétion d'insuline sur la concentration en 3,′5′-AMP du foie et du tissu adipeux, le métabolisme du glycogène et la lipolyse peuvent s'adapter rapidement à la prise de nourriture.
    Abstract: Zusammenfassung An der Steigerung der Glykogensynthese der Leber und der Verminderung der Lipolyse durch Insulin ist eine Abnahme der 3′,5′-AMP-Konzentration wesentlich beteiligt. Die 3′,5′-AMP-Bildung ist in Fettgewebe, das mit Insulin inkubiert wird, vermindert. Insulin beeinflußt jedoch auch den 3′,5′-AMP-Abbau. -Die 3′,5′-AMP-Phosphodiesterase (PDE)-Aktivität des Fettgewebes, der Leber und, in geringerem Grade, der Skeletmuskulatur ist im Insulinmangel vermindert, d.h. bei alloxandiabetischen oder hungernden Ratten. I.v. Injektion von 0,5 E/kg Insulin oder eine erhöhte Abgabe von Insulin aus dem Pankreas nach Glucoseinjektion führen in diesen Geweben zu einem raschen Anstieg der PDE-Aktivität. Dieser ist in der Leber schon 15 min nach Insulingabe nachweisbar und erreicht nach 30–45 min sein Maximum. In der Niere ist kein Einfluß von Insulin auf die PDE-Aktivität nachweisbar. — Aus Rinderherz isolierte PDE wirdin vitro durch Insulin aktiviert, jedoch werden2 · 10−5 M zur Verdopplung der Aktivität benötigt. Actinomycin D verhindert die Steigerung der Leber-PDE-Aktivität nach Insulininjektion. So kann die Wirkung des Hormons im wesentlichen auf eine gesteigerte PDE-Synthese zurückgeführt werden. — Durch diesen Einfluß der Insulininkretion auf die 3′,5′-AMP-Konzentration in Leber und Fettgewebe können Glykogenstoffwechsel und Lipolyse rasch an die Nahrungsaufnahme angepaßt werden.
    Notes: Summary Influence of insulin on liver glycogen metabolism and on lipolysis appears to be mediated by a decreased intracellular 3′,5′-AMP concentration. Reduced formation of 3′,5′-AMP had been shown in adipose tissue incubated with insulin. The influence of insulin on 3′,5′-AMP degradation has been investigated. — 3′,5′-AMP phosphodiesterase (PDE) activity was reduced in liver, adipose tissue and, insignificantly, in skeletal muscle of insulin deficient, i.e. alloxan diabetic or starved rats. I.V. injection of a low dose of insulin (0.5 U/kg) or stimulation of endogenous insulin secretion by injection of glucose led to a rapid increase of PDE activity in these tissues. 15 min after insulin injection liver PDE activity was increased. The maximal effect occurred after 30–45 min. Renal PDE activity was not decreased in alloxan diabetes, insulin injection has been found ineffective. —In vitro, there was an activating effect of crystalline insulin on PDE purified from beef heart. Insulin concentration required for duplication of enzyme activity was of the order of 2 · 10−5 M. Treatment with actinomycin D nearly prevented stimulation of liver PDE by insulin. This may indicate that the action of insulin on PDE activity is essentially based on an increased enzyme synthesis. — Owing to the influence of insulin secretion on liver and adipose tissue 3′,5′-AMP concentration, glycogen metabolism and lipolysis can be quickly adapted to food intake.
    Type of Medium: Electronic Resource
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