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  • 1995-1999
  • 1965-1969  (106)
  • 1968  (106)
  • Analytical Chemistry and Spectroscopy  (92)
  • Insulin  (14)
  • Nuclear reactions
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Years
  • 1995-1999
  • 1965-1969  (106)
Year
  • 1
    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.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 4 (1968), S. 1-9 
    ISSN: 1432-0428
    Keywords: Human growth hormone ; Growth hormone ; Insulin ; Diabetes mellitus ; Experimental diabetes ; Acromegaly ; Pathogenesis of diabetes mellitus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Il a été démontré récemment que l'hormone de croissance humaine (HGH) joue un rôle prééminent dans la régulation normale de la glycémie. De plus, il est bien connu que l'hormone de croissance peut créer un état semblable au diabète chez l'animal. Chez l'homme, l'injection de HGH ou l'hypersécrétion de l'hormone endogène dans l'acromégalie est suivie d'intolérance au glucose seulement dans 25% des cas. — Dans ce travail nous présentons des données qui mettent l'action dite diabétogène de HGH dans un contexte plus nuancé. Nous suggérons que HGH, bien que diminuant l'utilisation du glucose par les tissus périphériques, n'est pas une substance primairement diabétogène, car l'effet insulinotrope de l'hormone cause une hyperinsulinémie compensatrice, qui à son tour normalise la tolérance au glucose. HGH est diabétogène exclusivement chez les sujets prédiabétiques dont le pancréas est incapable de répondre à l'effet insulinotrope de l'hormone. Chez ces sujets, la diabétogénicité de HGH n'étant pas surmontée par une hyperinsulinémie compensatrice, la tolérance au glucose sera anormale. Ainsi, HGH peut être considérée comme unfacteur additif pour la pathogénèse du diabète sucré, la condition essentielle et primaire étant un état préexistant de prédiabète.
    Abstract: Zusammenfassung Wie kürzlich gezeigt wurde, spielt das menschliche Wachstumshormon (HGH) eine wichtige Rolle bei der Kontrolle der Blutzucker-Homöostase. Ferner ist schon lange bekannt, daß die Verabreichung von Wachstumshormon an Tiere zu einem diabetesähnlichen Zustand führen kann. Beim Menschen löst die Gabe der Substanz oder die Überproduktion des endogenen Hormons bei der Akromegalie nur in etwa 25 % der Fälle eine Glucosetoleranzstörung aus. — In dieser Arbeit werden Resultate beschrieben, die ein detaillierteres Bild der sogenannten diabetogenen Wirkung des HGH vermitteln. Wir möchten annehmen, daß das HGH, obwohl es den peripheren Glucoseverbraueh herabsetzt, kein primär diabetogener Faktor ist, da es über eine Insulin-mehrausschüttung zu einem Hyperinsulinismus führt, der eine normale Glucosetoleranz bewirkt. HGH zeigt Scine diabetogene Wirkung nur bei Prädiabetikern, deren Pankreas den stimulierenden Effekt des Hormons auf die Insulinausschüttung nicht beantworten kann. Bei diesen Personen kann eine Störung der Glucosetoleranz dadurch entstehen, daß die diabetogene Wirkung des HGH nicht durch einen kompensatorischen Hyperinsulinismus ausgeglichen wird. HGH kann daher als ein Zusatzfaktor bei der Diabetesentstehung angesehen werden, deren Hauptvorbedingung jedoch eine schon vorher bestehende prädiabetische Stoffwechselsituation darstellt.
    Notes: Summary Human growth hormone (HGH) has recently been shown to play a prominent role in the control of blood glucose homeostasis. Furthermore, it has long been known that administration of growth hormone in animals can induce a diabetes-like state. In human subjects, exogenous administration of HGH or hypersecretion of the endogenous hormone in acromegaly is accompanied by glucose intolerance in only about 25 per cent of the cases. — In this paper, data are presented which give a more diversified picture of the so-called diabetogenic action of HGH. It is suggested that HGH, although decreasing the peripheral utilization of glucose, is not a primary diabetogenic factor, since its insulinogenic action causes a compensatory hyperinsulinism, with normal glucose tolerance as the result. HGH is diabetogenic only in prediabetic subjects whose pancreas is unable to respond to the insulinogenic effect of the hormone. In such subjects, the diabetogenic action of HGH not being counterbalanced by a compensatory hyperinsulinism, glucose intolerance may result. Thus, HGH may be regarded as anadditional factor for the development of diabetes, the major prerequisite being a preëxisting prediabetic state.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 4 (1968), S. 111-117 
    ISSN: 1432-0428
    Keywords: Insulin ; diabetes ; insulinase ; rat diaphragm ; glycogen synthesis ; RNA turnover ; cell culture ; anti-insulin serum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Peu de progrès conduisant à la compréhension du diabète en termes moléculaires ont été réalisés. La possibilité qu'il existe une modification dans la structure de l'insuline des diabétiques, aussi bien circulante que pancréatique, s'appuie sur trois arguments expérimentaux obtenus au laboratoire des auteurs. — La purification immunochimique de l'insuline circulante de diabétiques jeunes non traités par l'insuline a d'abord conduit à la constatation que cette insuline est relativement résistante à l'action réductrice et protéolytique d'une préparation d'insulinase musculaire. De plus, l'insuline pancréatique, isolée à partir de cinq pancréas diabétiques, s'est avérée d'activité biologique diminuée quant à son pouvoir d'augmenter la synthèse du glycogènein vivo et à sa capacité d'accélérer le “turnover” du R.N.A. en culture tissulaire. — La nature de cette „insuline anormale” et son rôle possible dans la physiopathologie du diabète sont examinés à la lumière de la nécessité de donner une définition spécifique de la modification moléculaire précise.
    Abstract: Zusammenfassung Unsere Kenntnisse über den Diabetes in molekularbiologischer Sicht haben kaum Fortschritte gemacht. Die Möglichkeit, daß das zirkulierende und das Pankreas-Insulin des Diabetikers strukturelle Unterschiede aufweisen, wird durch die Ergebnisse von drei verschiedenen Untersuchungsreihen gestützt, die im Laboratorium der Verfasser durchgeführt wurden. — Immunologisch gereinigtes zirkulierendes Insulin von Diabetikern, die noch kein Insulin erhalten hatten, erwies sich als recht widerstandsfähig gegenüber dem Abbau durch ein Insulinase-Rohextrakt aus Muskelgewebe. Aus den Bauchspeicheldrüsen von 5 Diabetikern gewonnenes Insulin zeigte sowohl in seiner Fähigkeit, die Glycogen-Synthesein vivo, als auch den Ribonucleinsäuren-Umsatz in der Gewebskultur zu stimulieren, eine herabgesetzte biologische Aktivität. — Bei der Diskussion der Natur dieses „abnormen” Insulins und seiner hypothetischen Rolle in der Physiopathologie des Diabetes ergibt sich besonders deutlich, wie dringend erforderlich eine genauere Klärung des in diesem Falle vorliegenden molekularen Umbaus ist.
    Notes: Summary Understanding of diabetes in molecular terms has advanced very little. The possibility that a structural difference exists in the circulating and pancreatic insulin moiety of diabetics is supported by three lines of evidence obtained in the authors' laboratory. — Immunologically purified circulating insulin from diabetic subjects untreated with insulin was noted to be relatively resistant to degradation by a crude muscle insulinase preparation. The pancreatic insulin of five diabetic pancreases was found to have a decreased biological activity in its ability to enhance glycogen synthesisin vivo and in its capacity to stimulate RNA turnover in tissue culture. — The nature of this “abnormal insulin” and its hypothetical role in the physiopathology of diabetes are discussed in the light of the need for a specific definition of the precise molecular change.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 4 (1968), S. 68-70 
    ISSN: 1432-0428
    Keywords: Insulin ; proinsulin ; biosynthesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Après incubation de tranches de pancréas d'embryon de veau, la leucine-H3 est incorporée dans une fraction protéique qui semble avoir les propriétés d'une “proinsuline”. Cette fraction protéique est de taille supérieure à l'insuline, possède l'immunoréactivité propre à l'insuline, et après traitement limité par la trypsine elle est transformée en un peptide semblable à l'insuline.
    Abstract: Zusammenfassung Die Inkubierung von Dünnschnitten des fötalen Rinder-Pankreas in Gegenwart vom H3- Leucin ergab einen Einbau dieser Amminosäure in eine Eiweißfraktion, die die Eigenschaften eines, Pro-Insulins' aufwies. Das Molekulargewicht dieser Eiweißfraktion war größer als dasjenige des Insulins; sie besaß die Immunreaktivität des Insulins und konnte durch teilweisen Abbau mit Trypsin in ein insulinähnliches Peptid umgewandelt werden.
    Notes: Summary Incubation of fœtal bovine pancreas slices resulted in the incorporation of3H-leucine into a protein fraction which appeared to have the properties of a ‘proinsulin’. This protein fraction was larger in size than insulin, possessed the immunoreactivity of insulin and was converted by limited trypsin treatment to a peptide similar to insulin.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 4 (1968), S. 281-285 
    ISSN: 1432-0428
    Keywords: Insulin ; radioimmunoassay ; bile ; bile acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé L'effet des acides biliaires sur le dosage radioimmunologique de l'insuline a été examiné et les résultats ont montré que les acides biliaires en concentrations physiologiques nuisent à la liaison de l'insuline avec le sérum anti-insulinique. La courbe de dilution de l'insuline immunoréaetive dans la bile de la vésicule biliaire porcine n'était pas parallèle à celle de l'insuline porcine standard. Après extraction de la bile porcine par du sérum antiinsulinique et après dosage de l'extrait, des taux d'insuline plus bas ont été trouvés. Les résultats suggèrent qu'une partie seulement de «l'insuline immunoreactive» de la bile de la vésicule biliaire représente de l'insuline véritable.
    Abstract: Zusammenfassung Die Wirkung von Gallensäuren auf die radio-immunologische Insulinbestimmung wurde untersucht. Aus den Resultaten geht hervor, daß Gallensäuren in physiologischen Konzentrationen zu einer Störung der Insulinbindung an Anti-Insulinserum führen. Die Verdünnungskurve von immunoreaktivem Insulin im Gallensaft aus Schweinegallenblasen verlief nicht parallel zur Standard-Eichkurve von Schweineinsulin. Nach Extraktion der Schweinegalle mit Anti-Insulinserum fanden sich im Extrakt niedrigere Insulinkonzentrationen. Die Ergebnisse deuten darauf hin, daß nur ein Teil des „immunoreaktiven Insulins” in der Blasengalle echtes Insulin ist.
    Notes: Summary The effect of bile acids on the radioimmunoassay of insulin has been investigated, and the results show that bile acids in physiological concentrations interfere with the binding of insulin by anti-insulin serum. The dilution curve of immunoreactive insulin in pig gall-bladder bile was not parallel to that of standard pig insulin. After extraction of pig bile with anti-insulin serum and assay of the extract, lower insulin levels were found. The results suggest that only a part of the “immunoreactive insulin” in gall-bladder bile is genuine insulin.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Pflügers Archiv 301 (1968), S. 254-258 
    ISSN: 1432-2013
    Keywords: Insulin ; Potassium Deficiency ; Membrane Potential ; Rat Diaphragm ; Insulin ; Kaliummangel ; Membranpotential ; Rattenzwerchfell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung An 102 Zellen des Zwerchfells von insgesamt 7 Ratten mit alimentärem Kaliummangel fanden wir unter dem Einfluß von Insulin (0,1 I.E./ml) eine Depolarisation um 11,2 mV, nämlich von −94,6 (s=±6,4) mV bei insgesamt 100 Zellen auf −83,4 (s=±6,8)mV (p 〈 0,001). Die Kaliumkonzentration in der Inkubationslösung betrug 4,7 (s=±0,29) mval/l. — Ferner steigt die bei kaliumverarmten Tieren erniedrigte intracelluläre Kaliumkonzentration unter Insulineinfluß von 107 (s=±12) mval/lH2O IZR auf 130 (s=±19,8) mval/lH2O IZR an (p〈0,05). Die Befunde sprechen dafür, daß Insulin bei kaliumverarmten Tieren einen Netto-Kaliumeinstrom bewirkt, der eine Abnahme des Membranpotentials zur Folge hat.
    Notes: Summary In 102 single muscle cells of 7 rats with alimentary potassium depletion we found under influence of insulin (0.1 I.U./ml) a depolarisation of 11.2 mV, i.e. from −94.6 (s=±6.4)mV (100 cells) to −83.4 (s=±6.8)mV (p〈0.001). The potassium concentration in the incubation medium was 4.7 (s=±0.29) mequ/l. — In addition we measured under influence of insulin (0.1 I.U./ml) an intracellular potassium concentration of 130 mval/lH2O IZR, which is probably higher than in potassium deficient animals without insulin (p〈0.05). These findings suggest that insulin produces a netto potassium influx in potassium deficient animals, which could explain the depolarisation.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 10
    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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  • 11
    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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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Clinical and experimental medicine 148 (1968), S. 22-27 
    ISSN: 1591-9528
    Keywords: Insulin ; Hypoglycemia ; Xylitol ; Insulin ; Hypoglykämie ; Xylit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Bei Kaninchen, Meerschweinchen, Mäusen und Ratten wurde der Einfluß von Xylit auf die Insulinhypoglykämie untersucht. Es zeigte sich, daß Xylit die durch große intravenöse Insulindosen hervorgerufenen neurogenen Störungen (Lähmungserscheinungen, Krämpfe) zu beseitigen bzw. zu verhüten vermag. Gleichzeitig kommt es zu einem Wiederanstieg der Glucosekonzentration im Blut. Die möglichen Mechanismen dieser Wirkung werden diskutiert.
    Notes: Summary The influence of xylitol on insulin-induced hypoglycemia was studied in rabbits, guinea pigs, mice, and rats. Relief of hypoglycemia and the concomitant disturbances of the nervous system was observed following the injection of xylitol. The possible mechanisms of this action are discussed.
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  • 14
    ISSN: 1591-9528
    Keywords: Insulin ; Monosaccharide ; Hormones ; Mammals ; Amphibians ; Insulinsekretion ; Monosaccharide ; Hormone ; Säugetiere ; Amphibien
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die Stimulierung der Insulinsekretion durch Monosaccharide und Hormone wurde mit der Technik der Inkubation von isolierten Pankreasstückchen untersucht. Der Insulingehalt der Inkubationsmedien und der Pankreasgewebe wurde mit der biologischen (Oxydation von14C-Glucose durch das epidydemale Fettgewebe der Ratte) und der radioimmunologischen Bestimmungsmethode mit Trennung des freien und gebundenen Insulins durch Amberlite ermittelt. Das Kaninchenpankreas reagierte auf Glucose, Fructose, Ribose, Xylose, STH und Sekretin mit gleichbleibender Insulinausschüttung, nicht dagegen auf Galaktose, D- und L-Arabinose und ACTH. Die Gewebe anderer Säugetiere (Hund und Kalb, nicht aber Ratten) und einer Amphibienart (Grasfrosch) zeigten eine übereinstimmende Insulinfreisetzung nach Gabe von Glucose, wobei die Säugetiere etwa 1%, das Amphibium etwa 10% des Insulingehalts abgaben. Das Froschpankreas wies in seiner Reaktion eine jahreszeitliche Abhängigkeit auf, indem es im Winter nicht, im Sommer am stärksten auf die Stimulationsreize ansprach.
    Notes: Summary The stimulation of insulin-secretion by monosaccharides and hormones was studied with the technique of incubation of isolated pieces of pancreas. The insulin content of the incubation medium and of the pancreatic tissue was measured using both biological (oxidation of 14-C-glucose by epidydimal fat tissue of rats) and radio-immunological methods (separation of free and bound insulin with amberlite). The rabbit pancreas was stimulated by glucose, fructose, ribose, xylose (with constant insulin release), STH, and secretin, but not by galactose,d- andl-arabinose, and ACTH. The pancreatic tissue of other mammals (dog and calf, not rats) and one amphibian species (gras frog) showed the same insulin release after glucose which was 1% by mammals and 10% by amphibian of the insulin content of the tissue. The reaction of the frog pancreas depended upon the time of the year. In summer it reacted strongly to stimulants but in the winter it did not.
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  • 15
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 61-70 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectral fragmentations of stereoisomeric cyclohexane-1,2-diols, p-menthane-2,3-diols, 1-hydroxycarvomenthols and 4-hydroxymenthols are discussed.
    Additional Material: 4 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 127-137 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Examination of a large number of spectra indicates that bis-unsaturated compounds commonly undergo a skeletal rearrangement in which part or all or the bridging moiety is eliminated, often with concomitant loss of hydrogen atoms. The spectra of labeled azobenzene, diphenyl sulfide, and their p,p′-dimethyl derivatives show that scrambling of hydrogen atoms precedes or accompanies such rearrangements, in contrast to the loss of a p-methyl group from the latter derivatives. These results are rationalized in terms of the radical site formed on one unsaturated functional group attacking the polarizable π-electrons of the other unsaturated group.
    Additional Material: 3 Tab.
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  • 17
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 87-113 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The thermal excitation energy of molecules greatly influences multistep degradation reactions of aliphatic compounds in the mass spectrometer. Molecules very often obtain their thermal excitation energy only within the ion source by wall collisions. Since it is not usually possible to keep the ion source temperature entirely constant the peak intensities in the spectra of one and the same compound differ considerably. Attention should be paid to this fact in the preparation of mass spectra collections.Multistep degradation reactions may be influenced by reduction of the electron energy and the ion source temperature such that only primary degradation products are preferentially formed. The interpretation of such spectra is easier. This technique was used to study the fragmentation reactions of bi-functional aliphatic compounds. It was shown that nearly all fragments can be deduced from molecular ion species, ionized at one or other functional group. Depending on the amount of fragments produced by ionization at the functional group it is possible to compare the iniluence of the various substituents on the fragmentation, and to rank them according to their increasing influence on the fragmentation as shown:
    Notes: Die thermische Anregungsenergie der Moleküle beeinflußt mehrstufige Abbaureaktionen aliphatischer Verbindungen im massenspektrometer sehr stark. Thermische Anregung erhalten die Moleküle vielfach erst durch Wandstöße in der Ionenquelle. Da in den Wenigsten Fällen die Ionenquellentemperature völlig konstant gehalten werden kann, unterscheiden sich Spektren ein und derselben Verbindung oft in ihren Intensitätwerten voneinander. Diesem Umstand sollte bei der Anlage von Spektrensammlungen Rechnung getragen werden.Durch Erniedrigung von Elektronenenergie und Ionenquellentemperatur lassen sich mehrstufige Abbaureaktionen os lenken, daß vorzugsweise nur primäre Spaltprodukte entstehen. Die Spektren werden dadurch qualitativ besser auswertbar. Bie Anwendung dieses Verfahrens auf bifunktionelle aliphatische Verbindungen Können nahezu sämtliche Spaltstücke ovn Molekülionenspezies abgeleitet werden, die an der einen oder anderen funktionellen Gruppe ionisiert wurden. Je nach der Mange der durch Ionisation an einer der Gruppen entstandenen Fragmente kann man daher den Einfluß der Substituenten miteinander vergleichen und diese nach steigender Einflußnahme auf die Bruchstückbildung in einer Reihen anordnen. Es ergibt sich danach etwa die folgende Reihung:
    Additional Material: 16 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 151-166 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of the different forms of vitamin B6, some metabolites and antimetabolites, and some analogs are reported. The free bases are suitable for study, but the 5-phosphates are not sufficiently volatile. The hydrochloride salts dissociate thermally in the inlet system into the free base and HCl and give the spectrum of the free base with the spectrum of HCL superimposed on it. The compounds studied are: pyridoxol, pyridoxamine and pyridoxal, which are different forms of vitamin B6; 4-pyridoxic acid and its lactone, 5-pyridoxic acid lactone, isopyridoxal, 5-formyl-3-hydroxy-2-methylpyridine-4-carboxylic acid, and 3-hydroxy-2-methylpyridine-4,5-dicarboxylic acid, which are vitamin B6 metabolites; α4-and α5-deoxypyridoxol, 3-deoxypyridoxol, and 4- and 5- norpyridoxol, which are antimetabolites and analogs of vitamin B6.
    Additional Material: 14 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 167-168 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new type of ion detector has been developed that can be made to operate in two ways. It can detect all ions, or it can be made to detect only those within a preselected energy range. Its use on a mass spectrometer to examine the metastable spectra of cis- and trans-butenes is described.
    Additional Material: 2 Tab.
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  • 20
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 169-187 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of guanidine and ten of its derivatives have been studied under both high and low resolution conditions. Evidence was detected for the migration of methyl groups, the formation of intermediate three-membered ring structures and decompositions involving expulsion of N. with release of kinetic energy.
    Additional Material: 13 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 199-204 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three isomeric compounds, I, II and III, were prepared and their mass spectra recorded. Comparisons of the spectra showed that the fragmentation of I proceeds only by way of II, and that II itself is transformed in part to III upon electron impact. It is suggested that selective ionization of each one of the two isolated functional groups in II may afford two isomeric radical ions, IIa and IIb. A possible interrelation to the photochemistry of these compounds is also discussed.
    Additional Material: 3 Ill.
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  • 22
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of three methoxypulvic dilactones, four methyl esters of methoxypulvic acids and five methyl ethers of pulvic acid derivatives have been measured and rationalised employing accurate mass measurements and metastable peak assignments to substantiate the proposed fragmentations and rearrangements. In particular, the mass spectral differences and similarities between the isomeric methoxypulvic dilactones, between their methanolysis products and between the isomeric methyl ethers, are rationalised.
    Additional Material: 10 Ill.
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  • 23
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of twenty three azetidines and seventeen 2-azetidinones are reported and discussed. The majority of spectra contain molecular ions. Fragmentation modes are largely dependent upon the substitution pattern and involve specific cleavage of the four-membered ring. Several hydrogen rearrangement reactions occur, and in some cases, cis and trans isomers may be distinguished by large differences in the relative abundances of certain fragment ions.
    Additional Material: 16 Ill.
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  • 24
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The formation of 1,1-dimethoxy-alkyl rearrangement ions in the mass spectra of methyl ethers of linear diols, 1,2,3-triols and of derivatives of pentaglycerol and pentaerythritol has been investigated by deuterium labelling and mass measurements. Methoxy group migrations do not occur, or at least only to a small amount, in the mass spectra of the diol-dimethyl ethers. The mass spectra of methyl ethers of 1,2,3-triols exhibit characteristic peaks of the rearrangement ions +CH(OCH3)2 and +CR(OCH3)2. These ions arise by a 1,3-migration of a methoxy group, probably during a one step degradation of the molecular ion to give a molecule methyl alkenyl ether and a H-atom or alkyl radical as neutral fragments. Large peaks of the rearrangement ion +CH(OCH3)2 are observed in the mass spectra of compounds of the following type: A radical ion, formed by loss of HY from the molecular ion, rearranges by methoxy group migration in the mass spectra of these substances. Rearrangement by migration of hydroxy and acetoxy groups are also observed, but no migration of a Cl-atom.
    Notes: Die Bildung von 1,1-Dimethoxyalky-umlagerungsionen in den Massenspektren der Metyläther von linearen Diolen, 1,2,3-Triolen und Derivaten der verzweigten Polyole Pentaglycerin und Pentaerythrit wird mit Hilfe von Markierungen mit Deuterium und Massefeinbestimmungen untersucht. Methoxygruppenwanderungen treten in den Massenspektren der Dioldimethyläther nicht oder nur in sehr geringem Ausmaß auf. Die Massenspektren der 1,2,3-Trioltrimethyläther besizen aber charakteristische Peaks der umlagerungsionen +CH(OCH3)2 und +CR(OCH3)2. Diese Ionen entstehen durch eine 1,3-Wanderung einer Methoxygruppe, wahrscheinlich bei einem einstufigen Zerfall der Molekül-Ionen unter Bildung von Methyl-alkenyl-äther und H-Atom bzw. Alkylradikal als neutrale Fragmente. Gorße Peaks der Umlagerungsionen +CH(OCH3)2 werden in den Massenspektren von Verbindungen des Typs gefunde. Bei diesen Verbindungen wandert eine Methoxygruppe beim weiteren Zerfall von Radikal-Ionen, die durch Abspaltung von HY aus den Molekül-Ionen entstehen. Wanderungen von Hydroxy- und Acetoxy-Gruppen werden ebenfalls beobachtet, aber keine Wanderung von Cl-Atomen.
    Additional Material: 14 Ill.
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  • 25
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of tetronic acid and of a number of its derivatives are recorded and discussed. Where necessary, the composition of the fragment ions has been checked by high resolution mass measurements. Fragmentation of the molecular ion is explained in terms of the rupture of a bond attached to C-4, and the predominant routes for many of the compounds can be explained on the basis of two schemes, the first involving preliminary ketonisation of the molecular ion, followed by elimination of carbon monoxide, the second involving rupture of the C-4—R3 bond prior to elimination of carbon monoxide. Special structural features, however, provide alternative routes.
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  • 26
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    Biological Mass Spectrometry 1 (1968), S. 617-626 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The mass spectra of secondary vinylcarbinols of the structure R—CH(OH)—CH=CH2 show the same fragments as those of the isomeric ethylketones R—CO—C2H5. This is the result of a rearrangement of the molecular ions of the vinylcarbinols to molecular ions of the ethylketones before fragmentation occurs. Compounds of the two classes differ only slightly from one another in the intensity values.
    Notes: Die Massenspektren sekundärer des Typs R—CH(OH)—CH=CH2 zeigen die gleichen Bruchstücke wie die der isomeren Äthylketone R—CO—C2H5. Dies ist auf eine Umlagerung der Molekülionen der Vinylcarbinole in solche der Äthylktone vor Eintritt der Bruchstückbildung zurückzuführen. Die Massenspektren beider Verbindungsklassen unterscheiden sich nur geringfügig in den Intensitätswerten.
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  • 27
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some esters of γ, δ-unsaturated or β-arylsubstituted acids undergo a peculiar transformation under electron-impact including an elimination of the alcohol residue as a radical R. with the following loss of the ketene molecule. One of the oxygen atoms of the carbonyl group enters an ion which is formed from an unsaturated part of the molecule. The possible mechanism of this reaction and the influence of structural modifications on the course of this process are discussed.
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  • 28
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    Biological Mass Spectrometry 1 (1968), S. 915-917 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electron-impact induced loss of CO2 from phthalanil and 4-phthalimidobiphenyl is paralleled by the formation of large amounts of CO2 on pyrolysis. CO is also a major pyrolysis product, but the loss of CO from these compounds under electron-impact is not an important fragmentation process.The mass spectra of meta and para-chlorophthalanils show prominent [M — CO2] peaks but the corresponding peak for the ortho isomer is of relatively low intensity. CO and CO2 are the principal gaseous products of the thermal decomposition of o-chlorophthalanil.
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  • 29
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    Biological Mass Spectrometry 1 (1968), S. 1-1 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 30
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In spite of previous extensive studies on the mass spectrometry of alkyl cyanides, no good mechanistic insight has as yet been gained into the behavior of straight chain alky1 cyanides. For this reason the possible origins for the principal ions in the mass spectrum of a typical alkyl cyanide (n-hexyl cyanide) have been determined using high resolution mass spectrometry anddeuterium labeling of every carbon atom. The results lead to the conclusion that most of the typical fragmentation processes of n-alkyl cyanides proceed through cyclic intermediates.
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  • 31
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of nine bridged polycyclic chlorinated pesticidal compounds have been investigated, and fragmentation modes to account for the more abundant ions are postulated. The principal features of the spectra are ions corresponding to a set of retro-Diels-Alder decompositions, ions resulting from successive losses of Cl, HCl, or both, ions produced by combinations of a retro-Diels-Alder process with a preliminary or subsequent loss of Cl or HCl, and ions whose processes of formation more specifically involve the epoxide group.
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  • 32
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    Biological Mass Spectrometry 1 (1968), S. xi 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 33
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    Biological Mass Spectrometry 1 (1968), S. 425-445 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An investigation of the mass spectra of substituted benzophenones has shown that a number of rearrangement processes are operative. The rearrangements have been shown to involve solely the ortho-substituents to the carbonyl group and in many cases the carbonyl oxygen atom itself participates in the processes. Deuterium labelling experiments combined with data obtained from accurate mass and metastable analysis have enabled the probable mechanisms of rearrangement and fragmentation to be elucidated. An understanding of these processes should greatly assist in the location of substituents in unknown benzophenones.
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  • 34
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    Biological Mass Spectrometry 1 (1968), S. 459-465 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of B substituted 2,5-dimethyl cyclotetrazenoboranes have been studied. The compounds Me2N4BD, Me2N4BEt, Me2N4BVi, Me2N4BCl and Me2N4BBr give confirmatory evidence that loss of N2+H. from the system occurs by loss of H from the side chain and that the B—R bond is very stable under electron impact conditions. Fragmentation proceeds in a similar fashion to that of the 2,5-dimethyl substituted compounds with H bonded to the boron atom.
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  • 35
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    Biological Mass Spectrometry 1 (1968) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 36
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    Biological Mass Spectrometry 1 (1968), S. 487-502 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 37
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mass spectra of trimethylsilyl (TMS) derivatives of long chain dicarboxylic acids, hydroxy acids, cyano acids, and terminal diols, dithiols and diamines have been examined. A number of fragmentation pathways involving rearrangement of partial or intact TMS groups between the termini or remote points in the chain have been determined, using deuterium and carbon-13 labeling, and high resolution mass spectrometry. Knowledge of the occurrence of functional group migrations of this type is essential to the correct interpretation of mass spectra of TMS derivatives, which are now in wide use in mass spectrometry and gas chromatography. These data in addition provide further evidence for the general ability of remote functional groups to interact, by winding or coiling of long chains. A number of interesting doubly-charged ions are reported, in which the charges are reported, in which the charges are located at opposite ends of long chains, and for which no singly-charged counterparts are observed.
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  • 38
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    Biological Mass Spectrometry 1 (1968), S. 703-712 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of mono- and di-substituted alkyl and aryl imidazolines have been measured and the spectra analysed with the aid of deuterium labelling and high resolution techiques.In contrast to the fragmentation of thiazolines, all principal fragments of the imidazoline ring contain one nitrogen with or without hydrogen migration. In the case of 2,4-disubstituted imidazolines, the presence of two tautomeric molecular ions are suggested.
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  • 39
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    Biological Mass Spectrometry 1 (1968), S. 741-743 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 40
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    Biological Mass Spectrometry 1 (1968), S. 761-775 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of two fungal metabolites, aspertetronin A and B, have been examined in conjunction with a series of tetronic acids and related compounds, and as a result the major modes of fragmentation of the tetronic acid ring system have been determined. Several substituent dependent rearrangements have also been recognised during this investigation which should prove useful in the structural elucidation of unknown compounds.
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  • 41
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    Biological Mass Spectrometry 1 (1968), S. 417-423 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The most prominent ion in the mass spectra of C6F5CH2X (X = H, Br, CH:CH2, COCl, and CH2C6F5) is C7F5H2+, formulated as the pentafluorotropylium cation. This ion is also found, in an amount comparable to the parent ion, in the spectrum of (C6F5)2CH2. The heptafluorotropylium cation is found similarly in the spectrum of C6F5CF3. The mass spectra of (C6F5)2CHBr and [(C6H5)2CH]2 exhibit an ion C13F10H+ as the base peak, which is probably a pentafluorophenylpentafluorotropylium cation.The alcohol (C6F5)2CHOH shows loss of C6F5, followed by 2H, as a major breakdown pathway.The mode of formation, and the subsequent fragmentation, of the major ions in these spectra, are discussed.
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  • 42
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    Biological Mass Spectrometry 1 (1968), S. 447-458 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An investigation of the mass spectra of a number of substituted diphenyl ethers has shown that the major fragment ions are commonly due to cleavage of the molecule into the two benzene ‘half’ fragments although in many cases the molecular ion is the most abundant species observed.Little evidence is seen of M—CO or M—CHO peaks in these molecules but a large number of different rearrangement processes have been observed which involve ortho-substituents. These rearrangement ions, although in some cases not very abundant, can be diagnostic in the problem of locating substituents in the diphenyl ether nucleus.
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  • 43
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    Biological Mass Spectrometry 1 (1968), S. 483-485 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 44
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    Biological Mass Spectrometry 1 (1968), S. 467-481 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of a series of isatin, oxindole and 2-oxo-3-indolyl derivatives have been investigated using high resolution and deuterium labelling techniques. The fragmentations involve the sequential loss of a number of neutral molecules and the results show that the concept of charge localisation can be applied with success to explain the fragmentation processes even in these polyheteroatom species.
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  • 45
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    Biological Mass Spectrometry 1 (1968) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 46
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of nineteen aliphatic 1,2-glycols containing a variety of substituents have been recorded and mechanistic rationalizations are presented for the more important degradation processes observed. Fragmentation of the hydroxylated carbon-carbon bond in these compounds occurred to an appreciable degree often accompanied by the transfer of a hydroxylic hydrogen atom.
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  • 47
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bitter compounds isolated from the species Simaroubaceae represent a new family of degraded triterpenoids. Ailanthone, glaucarubolone and chaparrinone having a C20 skeleton belong to this family and their structures were previously determined. Mass spectra of these compounds and some of their derivatives have now been studied in detail and the results obtained are discussed in this communication. The observed fragmentation pattern is characteristic of the structural features of this group of compounds.
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  • 48
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    Biological Mass Spectrometry 1 (1968), S. 891-898 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The mass spectra of trimethylalkoxy silanes (CH3)3Si—O—(CH2)n—CH3 (n = 0-8) and (CH3)3Si—O—(CH2)n—CH(CH3)2 (n = 0-3) have been investigated and most of the fragmentations, induced by electron-impact, have been identified by metastable ions. The fragmentation mechanisms of trimethylpentoxysilane, established by Diekman, Thomson and Djerassi, are also observed in the mass spectra of these trimethylalkoxy silanes. Characteristic features of these reactions in the mass spectra of compounds with smaller and longer alkoxy groups, together with some additional fragmentations, are discussed.
    Notes: Es werden die Massenspektren von Trimethylaklkoxysilanen dr Typen (CH3)3Si—O—(CH2)n—CH3 (n = 0-8) und (CH3)3Si—O—(CH2)n—CH(CH3)2 (n = 0-3) wiedergegeben und die meisten Abbaureaktionen der Verbindungen bei Elektronenstoß durch metastabile Ionen belegt. Die von Diekman, Thomoson und Djerassi für Trimethypentoxysilane angegebenen Zerallsmechanisman laufen auch bei den untersuchten Substanzen ab. Es werden Besonderheiten beim Ablauf dieser Reaktionen bei Trimethylalkoxsilanen mit längerer und kürzerer Alkoxykette diskutiert und einige weitere Zerfallsreaktionen mitgeteilt.
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  • 49
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Après avoir identifié les impuretés qui accompagnent l'o-terphényle (I) marqué au 13C en position 2, c'est-à-dire, o-xenylcyclohexanol (II), o-xenylcyclohexène (III), hexahydrotriphénylène (IV) et o-xenylcyclohexane on a étudié la fragmentation des molécules I, II et IV, sous impact électronique, en tirant profit du marquage de ces molécules par le 13C.L'étude, par spectrométrje de masse, a été effectuée sur un instrument AEI MS9 pour ce qui regarde la composition atomique des ions principaux et sur un MAT CH-4 pour les déterminations quantitatives des espèces 12C et 13C, à basse énergie, en admettant une sensibilité égale.Le marquage par 13C de la position 2 dans I n'a pas encore mis clairement en évidence le réarrangement de cette molécule en une structure phénanthrénique après ouverture d'un noyau benzènique, comme le prévoyait une hypothèse formulée antérieurement à ce travail.La molécule II se fragmente suivant deux voies: I'une est formée d'une suite de fragments hydrocarbonés, produits à partir du pic moléculaire par perte de H2O et l'ature, d'une suite de fragments qui contiennent l'unique atome d'oxygène de la molécule. La différence dans le processus de fragmentation des deus séries s'explique par le fait que la perte d'une molécule d'eau, à partir de la molécule, stabilise les 2 atomes de carbone adjacents au C porteur du groupe - OH, le titre en 13C du fragment hydrocarboné en C15 étant relativement plus élevé que celui du fragment oxygéné à nombre égal d'atomes de C.Le marquage par 13C de la molécule IV montre comment se fait la rupture du cycle saturé sous bombardement électronique, le premier atome de C enlevé étant le plus proche du cycle centra.
    Notes: After identification of the impurities, separated from synthesized orthoterphenyl (I) labelled in position 2 with 13C, i.e. o-xenylcyclohexanol (II), o-xenylcyclohexene (III), hexahydrotriphenylene (IV) and o-xenylcyclohexane (V), the fragmentation processes under electron-impact of molecules I, II and IV have been studied, advantage being taken of their 13C labelling.Mass spectrometric studies were carried out on an AEI MS-9 for determination of the atomic composition of the main ions and on a MAT CH-4 instrument for quantitative determination of 12C and 13C species, at low energy, assuming an equal sensitivity.The 13C labelling of position 2 in I, has not yet given clear evidence of a formerly assumed rearrangement into phenanthrenic structure after ring opening.The fragmentation of molecule II occurs in two ways, i.e. into a series of hydrocarbon fragments, produced from the molecular ion by loss of H2O or into fragments still containing the oxygen atom. The difference between the fragmentation processes of the two series depends on the fact that the loss of H2O from the molecule stabilizes the two carbon atoms adjacent to the C carrying the hydroxyl group. This is shown by the relatively higher 13C content of the hydrocarbon fragment in C15 compared with that of the equivalent oxygenated fragment.The labelling in IV shows how the rupture of the saturated ring occurs under electron-impact, the first C removed being the one nearest to the central ring.
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  • 50
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    Biological Mass Spectrometry 1 (1968), S. 503-517 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of a series of alicyclic fluorocarbon complexes of manganese, rhenium, iron and ruthenium are described and discussed. It is shown that the breakdown of these complexes after ionization depends on the nature of the metal, and of the other groups attached to the metal. Effects due to elimination of metal halides, formation of metal fluoride ions, and ligand transfer reactions are found, and result in significant differences in the fragmentation patterns of the complexes from those of the parent fluorocarbons.
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  • 51
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    Biological Mass Spectrometry 1 (1968), S. 563-566 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass-spectral behaviour of long-chain aliphatic primary alcohols of the normal, iso-and anteiso-series have been discussed. The mass-spectral fragmentation of individual alcoholic types have been found to be structurally specific. The mass spectra of some deuterio derivatives have shown, however, the complicated nature of the fragmentation processes.
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  • 52
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    Biological Mass Spectrometry 1 (1968) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 53
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    Biological Mass Spectrometry 1 (1968), S. 583-592 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Skeletal rearrangement processes of the general type \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm ABC}^{\mathop {\rm + }\limits_{\rm .} } {\rm } \to {\rm AC}^{\mathop {\rm + }\limits_{\rm .} } {\rm + B} $\end{document} in which HCN is eliminated and also bond-forming reactions involving intramolecular aromatic substitution occur in aromatic azines upon electron impact. In addition, hydrogen rearrangements can lead to abundant benzonitrile and benzalimine molecular ions and their substituted analogues. The abundant [M—1] ions are predominantly formed by loss of the methine hydrogen preceded by complete scrambling of the aromatic and methine hydrogens. The similarities between the processes occurring in azines and those in anils, both in their normal bond cleavages and in some bond-forming reactions are emphasized.
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  • 54
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    Biological Mass Spectrometry 1 (1968), S. 613-615 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Migration of the heteroatom substituent is an important feature in the mass spectra of β-chloro- and β-hydroxy-ethyl aryl sulphones. In these compounds the migratory aptitude of the heteroatoms appears to be greater than that of the hydrogen atoms.
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  • 55
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    Biological Mass Spectrometry 1 (1968), S. 627-632 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fact that some αβ-unsaturated alcohols give mass spectra that bear some similarity with the corresponding saturated ketones is discussed, and the double hydrogen transfer necessary to accommodate this is examined by deuterium labelling.
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  • 56
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectral fragmentation of thiosemicarbazone derivatives of some typical aliphatic, alicyclic and aromatic aldehydes and ketones has been rationalized using high resolution mass spectrometry supplemented by deuterium labeling. Thiosemicarbazone derivatives of carbonyl compounds yield mass spectra which have little in common with those generated by their semicarbazone analogs.
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  • 57
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    Biological Mass Spectrometry 1 (1968), S. 739-740 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biological Mass Spectrometry 1 (1968), S. 713-737 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Fragmentation under electron impact of phenylhydrazones of aromatic aldehydes and ketones, of nitrostilbenes, nitrobenzalacetophenones and analogous compounds is determined by intramolecular oxidation reactions. Oxygen transfer from the o-nitrogroup on to the hydrazon- or stilbene-double bond is taking place; degradation of the resulting rearrangement products provides some of the most characteristic features in the mass spectra of such compounds. The spectra of 20 out of 40 compounds investigated are presented and discussed. Several other rearrangement reactions are observed. An additional conjugated double bond in the hydrazone chain completely changes the reactivity under electron impact. Even saturated substituents (cyclopropyl) can be drastically affected in their mode of fragmentation by an o-substituted nitrogroup.
    Notes: Die Fragmentierung von Nitrophenylhydrazonen aromatischer Aldehyde und Ketone, von Nitrostillbenen, Nitrobenzalacetophenonen und analogen Verbindungen unter Elektronenbeschuss wird entscheidend durch intramolekulare Oxidationsreaktionen beeinflusst, sofern sich eine Nitrogruppe in o-Stellung zum ungesättigten substituenten befindet. Es findet eine Sauerstoffübertragung von der o-Nitrogruppe auf die Hydrazon- oder Stilbendoppelbindung statt; ein wesentlicher Teil der charakterisierenden Fragmente in den Massenspektren dieser Verbindungen stammt aus dem Zerfall dieser Sauerstoffübertragungsprodukte. 20 Spektren von 40 untersuchten Verbindungen werden präsentiert und diskutiert. Eine Reihe weiterer umlagerungsreaktionen werden beobahtet. Eine konjugierte zusätzliche Dopplbindung in der Hydrazonkette ändert die Reaktivität der Verbindung vollsändig. auch die Fragmentierung gesättigter Substituenten (Cyclopropyl) kann durch eine o-Nitrogruppe entscheidend beeinflusst werden.
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  • 59
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In comparing N-acetylmorpholine to closely related systems, two major differences in fragmentation are observed. M-15 and M-43 fragments, although quite common to such systems, are unusual with respect to their genesis. Formation of the M-15 fragment by loss of C-3 instead of the anticipitated loss of C-2 or C-8 is evident from shifts in the spectra of deuterated analogs. The M-43 species arises from total loss of the N-acyl substituent rather than the usual two-step loss of ketene plus a ring hydrogen. These data are presented in support of mechanistic rationale involving radical induced ring contraction to a common intermediate molecular ion. Techniques of high resolution mass spectrometry and isotope labeling have been employed to substantiate certain mechanistic details.
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  • 60
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    Biological Mass Spectrometry 1 (1968) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
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    Biological Mass Spectrometry 1 (1968), S. 47-60 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The field ionization and electron impact mass spectra of some monoterpenes are compared. Some general rules applicable also to other substances are derived, summarizing the new structural information that can be obtained by combination of field ionization and electron impact data. The general conclusions are: (1) By comparison of FI and EI mass spectra one can recognize which of the most intense peaks in the EI mass spectra are originating from rearrangement or multistip dissociation processes on the one hand, or from simple direct bond rupture on the other hand. (2) The molecular weight of each substance containing C, H, O, N atoms (or some of them) can be determined unambiguously by field ionization, even if there is no parent peak detectable by electron impact. (3) Extremely strong metastable peaks in the FI mass spectrum are indicative of the splitting off of a polar group from a highly branched carbon atom, under rearrangement of the molecular ion. (4) Ions of about double the molecular weight are often found in the FI mass spectra if the molecule contains carbonyl or hydroxyl groups, or conjugated multiple bonds in aliphatic compounds.
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  • 62
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    Biological Mass Spectrometry 1 (1968), S. 115-126 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of a series of metal complexes of dibenzoylmethane have been rationalized. The paths of novel rearrangement reactions involving both hydrogen and oxygen migration may differ according to the type of metal atom in the complex. Further examples are proposed of the effect of metal valency changes in ion reactions.
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  • 63
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This book has been written with the intention of enabling the organic chemist to endeavor to interpret his own mass spectra and to decide whether mass spectrometry would be useful for his specific problems. Besides a description of experimental techniques the main body of the oeuvre consists of a thorough discussion of fragmentation processes triggered by various structural elements, followed by selected examples from miscellaneous classes of natural products. Of special value is a chapter on structure elucidation of unknown compounds. Each section also offers an ample list of literature references. The present book can be highly recommended as an introduction to organic mass spectrometry, yet it will prove useful also for those advanced in this art.
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  • 64
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    Biological Mass Spectrometry 1 (1968), S. 273-278 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of 1-phenylanthra-9,10-quinone and 20 substituted l-phenylanthraquinones having alkyl methoxyl, nitro and halogen substituents in the o-, m- and p-positions of the phenyl ring have been measured. The spectra are discussed with particular reference to the loss from the molecular ion of a hydrogen atom and of the substituent.
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  • 65
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    Biological Mass Spectrometry 1 (1968), S. 31-46 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 6 Ill.
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  • 66
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    Biological Mass Spectrometry 1 (1968), S. 13-29 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of a variety of alkyl and aryl oxazoles have been determined and the spectra analyzed with the aid of deuterium labelling and high resolution mass spectrometry. In contrast to the corresponding benzenoid compounds, the mass spectra of isomeric alkyl oxazoles are distinctive and in this respect are akin to those of the corresponding pyridines. Further analogy to the pyridines is suggested by the unfavorable nature of a carbonium ion adjacent to the 2-position and this effect may be used to locate alkyl substituents attached to the oxazole nucleus. The loss of carbon monoxide from the molecular ions of 2,5-disubstituted oxazoles probably occurs with ring opening and migration of the C-5 substituent (e.g.Br) to the C-4 position.
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  • 67
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    Biological Mass Spectrometry 1 (1968), S. 191-198 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectrum of 1-(2-thienyl) hexane-1-13C is reported. The principal fragmentation routes ofthe parent ion are delineated. Beta cleavage of the alkyl chain predominates, and the label retention indicates that the alpha carbon atom remains with the charged ring moiety. A substantial part of the m/e 97 ion undergoes a ring expansion to a six membered ring. A small amount of alpha cleavage of the alkyl chain occurs with the expected loss of the label. Further fragmentation of the ions from initial alpha or beta cleavage produces similar fragment ions. It is noted that many of the neutral particles lost in the formation of the fragment ions are typical of those encountered in the alkylbenzenes or other aromatic ion systems.
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  • 68
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    Biological Mass Spectrometry 1 (1968), S. 215-229 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A variety of metal-complexes with Corrin-type macrocyclic ligands and synthetic precursors thereof are investigated by mass spectrometry. Analytical results are obtained from thermal reactions in the inlet system and from electron-impact-induced fragmentations. The former yield information concerning identity of small ligands in octahedral Co(III)-complexes, of anions in complex-salts and the possibility of thermal cyclisation of open ligands, the latter provide molecular weights, a means of type analysis and theoretically interesting modes of fragmentation. An unprecedented subsequent loss of up to seven methyl-groups is observed. Different fragmentation-mechanisms and the possible influence of metal-valency-changes and even- or odd-electron-ion-features are discussed. Some of the metals like Zn and Na seem to be able to form different types of metal-ligand-bonds.
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  • 69
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    Biological Mass Spectrometry 1 (1968), S. 397-402 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Competing primary reactions by which 1-tetralone loses C2H4 and CO give rise to a doublet at mass 118 in the high-resolution mass spectrum corresponding to 96·4% C8H6O+ and 3·6% C9H10+, respectively. Study of the remainder of the spectrum however, suggests that these intensities constitute a poor measure of the relative importance of the two reaction paths. The C9H10+ ion evidently degrades more readily than C8H6O+, since an estimated 26% of the ions arising in these paths involve primary loss of CO. This estimate is supported by voltage dependence of the intensity distribution between the members of the doublet. As ionizing voltage is decreased, the intensity distribution is constant to about 20 volts, but between 20 and 10 volts the value for C9H10+ rises smoothly from about 3.5% to about 25%.
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  • 70
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    Biological Mass Spectrometry 1 (1968), S. 403-416 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectral fragmentations of the saturated five-, six- and seven-membered ring ethers have been determined by studying their site-specifically deuterated analogues by both high and low-resolution mass spectrometry.The initial processes, governing the fragmentations of the cyclic ethers are shown to be identical with the well-known processes of linear nonbranched ethers, i.e. predominant α-fisson in the lower members and predominant carbon-oxygen fisson with charge retention on the carbon atom in the higher members.
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  • 71
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    Biological Mass Spectrometry 1 (1968), S. 835-846 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of (π-C5H5)2Ti(C6F5)X (X = Cl and C6F5), C6F5Re(CO)5, RfFe(CO)2(π-C5H5) (Rf = C6F5, 4-HC6F4, and three isomeric H2C6F3), and C6F5Ru(CO)2(π-C5H5) are compared to those of C6F5X (X = F, Cl, Br, I) and the three isomers of C6F4H2. Significant differences occur, apparently depending on the relative thermodynamic stabilities of the various fragments which may be formed. Comparison of the mass spectra of pentafluorophenyl- and pentafluorobicyclo[2.2.0]hexa-2,5-dien-2-yl-Re(CO)5 show that similar ions are produced by both complexes, perhaps because of thermal isomerisation before ionisation.
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    Biological Mass Spectrometry 1 (1968), S. 907-909 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biological Mass Spectrometry 1 (1968), S. 913-914 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of esters of the general formula MeO2C·[CF2]n·CO2Me, n = 6 to 9, are reported and briefly discussed. Common features of the mass spectra are prominent peaks at [M — CO2], [M — CO2 — C2F4] and [M — CO2 — 2C2F4].
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  • 74
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    Biological Mass Spectrometry 1 (1968), S. 391-395 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Production of NO+- and NO2+- intermediate complexes formed by nitration of aromatic compounds by means of ion-molecule reactions in the gas phase were attempted. The experiments were performed with benzene, pyridine and toluene respectively and with NO+, NO2+ CH3NO2+ and CH2ONO2+ als ‘nitration’ ions. Aromatic NO+-as well as NO2+-complexes were observed with varying reaction cross-sections. The determined lower limit of bonding energy of 16 kcal/mol for to be σ-complexes. This fact was regarded as additional support for the analogy between electrophilic substitution reactions and ion-molecule reactions.
    Notes: Es wurde versucht, die bei der Nitrierung von Aromaten entstehenden NO+-bzw. NO2+-Intermediärkomplexe durch Ion-Molekül Reaktionen in der Gasphase zu erzeugen. Die utersuchungen erfolgten am Benzol. Pyridin und Toluol mit NO+, NO2+ sowie CH3NO2+ und CH2ONO2+ als ‘Nitrierungs’-Ionen. Es ließen sich sowohl aromatische NO+-Komplexe anchweisen mit wechselndem reaktionsquerschnitt. Die ermittelten unteren Grenzen der Bindungsenergien von 16 kcal/Mol für den NO+-Komplex und 29 kcal/Mol für den NO2+-Komplex legen es nahe, die nachgewiesenen Komplexe asl σ-Komplexe anzusehe, was als weiterer Hinweis für Analogie von elektrophilen Substitutionsreaktionen und Ion-Molekül-Reaktionen gewertet wird.
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  • 75
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mass spectra of 1-phenylethanol-1 and its analogues, specifically deuterated in the aliphatic chain, suggest that the [M—CH3]+ ion is represented partly by an α-hydroxybenzyl fragment. Moreover, the molecular ion loses successively - after scrambling of all hydrogen atoms, except those of CH3—a hydrogen atom and C6H6, generation the CH3CO+ ion.Diffuse peaks, found in the spectra of of 2-phenylethanol-1 and its analogues, specifically deuterated in the aliphatic chain and in the phenyl ring, show that the molecular ion loses C2H4O, possibly via a four-center mechanism, after an exchange of aromatic and hydroxylic hydrogens.Mass spectra of 1-phenylpropanol-2 and its analogues, specifically, deuterated in the aliphatic chain, demonstrate that in the molecular ion exclusively the hydroxyl hydrogen atom is transferred to one of the ortho-positions of the phenyl ring via a McLafferty rearrangement, generating the [M — C2H4O]+ ion. Furtherore, an eight-membered ring structure is proposed for the [M — CH3]+ ion to explain the loss of H2O and C2H2O from this ion after an extensive scrambling of hydrogen atoms.
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  • 76
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    Biological Mass Spectrometry 1 (1968), S. iv 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 77
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    Biological Mass Spectrometry 1 (1968), S. 527-530 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using energetic considerations, ketonic structures are postulated for the [M—olefin]+ fragments derived from alkoxybenzenes, alkylthiobenzenes and 9-ethoxyanthracene. Experimentally determined heats of formation for the tautomeric molecular ions derived from anthrone and 9-anthrol differ by 37 Kcal. mole-1.
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  • 78
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    Biological Mass Spectrometry 1 (1968), S. 519-525 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An ‘on-line’ mass spectrometer technique which permits the examination of the effects of radiation at short times has been used to study the radiolysis of methane by reactor radiation. The mass spectrometer used was the AEI MS-10. The experiments were carried out using the UTR-100 reactor at East Kilbride and the results using highly purified methane and methane with radical scavangers are described. With pure methane at 0·25% conversion, G-values of 0·36, 0·24, 0·07 and 0·03 were calculated for C3H8, C4H10, C5H12 and C6H14 respectively. No pressure-dependent reactions were observed in the pressure range 50 to 135 torr. The effects of radical scavengers were investigated and irradiation of methane containing 1 to 2% ethylene gave G-values for C2H6, C3H8, n-C4H10, iso-C4H10, C5H12 plus C6H14, C2H2, C3H6, C4H8 and C5H10 of 1·33, 2·02, 2·03, 0·35, 0·34, 0·30, 0·37, 0·90 and 0·31. The effects of adding 1 to 2% propylene and 1 to 2% oxygen were also examined and the results are described in the paper. Experiments with smaller quantities of oxygen emphasize the importance of removing all oxygen from the system before radiolysis begins. The paper then goes on to discuss in some detail the processes involved in the radiolysis of methane and concludes with suggestions for future work.
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    Biological Mass Spectrometry 1 (1968), S. 543-549 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: According to Stevenson's rule, there is a possibility that the chloromethyl and bromomethyl ions in the spectra of alkylhalides may not be formed from the molecular ion by processes described by electronic ground states alone. Since ion intensities at 75 eV are generally considered to be governed by appearance potentials, the operation of Stevenson's rule should influence correlations of intensity data according to the kinetic approach to mass spectra. Deviations from linearity were obtained in correlations of CH2Br+ intensities, but not in those of CH2CL+. Stevenson's rule is of help in explaining the deviations, but by its nature it is not absolute in predicting their occurrence with certainty. Consequently caution must be exercised in the interpretation of new data, particularly for aliphatic compounds.
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    Biological Mass Spectrometry 1 (1968), S. 551-561 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of usnic acid, decarbousnic acid, usnetic acid and usnetol are reported and mechanistically interpreted. The mass spectra of lichexanthone and lichexanthone methyl ether were also examined, and the unusal features of the latter spectrum have been rationalized.
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  • 81
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    Biological Mass Spectrometry 1 (1968), S. 567-581 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of twenty one C-19 modified cholesteryl derivatives have been determined and compared with results for related systems. In the case when the hydrogen(s) of the C-19 group have been replaced by other groups the metastable evidence shows that in those molecules with a C-3 hydroxyl group the loss of water followed by the loss of the C-19 group gives rise to an intense ion at m/e 353, whereas the loss of the C-19 group with hydrogen transfer to the ion, followed by the loss of water gives rise to the large ion at m/e 354. In contrast in the case of the C-3 acetates the main fragmentation is the loss of acetic acid followed by the loss of the C-19 group to give the ion at m/e 353. This is rationalised on the basis of results observed in other systems. In the case of the C-3 tosylates evidence for pyrolysis before electron impact fragmentation is presented. The subsequent fragmentation of the large ions at m/e 354, 353 and other m/e values in the high mass region is shown to be in line with earlier work.
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  • 82
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The mass spectra of 15 azines and 5 phosphazines are investigated by deuterium labelling and high resolution mass measurements. Azines of aldehydes undergo a skeletal rearrangement in which HCN and (HCN + H) are eliminated from the molecular ion. Azines of ketones first eliminate an aryl or alkyl radical and then rearrange with the expulsion of CN. or (CN. + H). Analogies to the photolytic or thermal elimination of nitrogen in azines could not be detected. o,o′-Dinitrobenzaldazin undergoes a double oxygen rearrangement in which carbon dioxide is eliminated. Phosphazines show a similar behaviour under electron-impact as under pyrolytic conditions.
    Notes: Die Massenspektren von 15 Azinen sowie 5 Phosphazinen werden mittels deuterium-Markierung und exakten Massenmessungen untersucht. Azine von Aldehyden eliminieren HCN und (HCN + H) aus dem Molekülion, was mit einer Umlagerung verbunden ist. Azine von Ketonen spalten zuerst ein Aryl-bzw. Akylradikal ab und lagern sich anschliessend um unter eliminieung von CN. oder (CN. + H). Analogien zur photolytischen oder termischen Abspaltungvon Stickstoff aus Azinen wurden nicht gefunden. o, o′-Dinitro-benzaldazin erleidet unter Elektronenstoss eine doppelte Sauerstoffumlagerung, bei de CO2 eliminiert wird. Phosphazine zeigen bei Elektronenbeschuss ein ähnliches Verhalten wie bei der Thermolyse.
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  • 83
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of various ring-substituted salicylic acids and derivatives thereof have been examined. Fragmentation pathways for derivatives of salicylic acid; 3-NO2 salicylic acid; 5-I salicylic acid; 3-NO2, 5-I salicylic acid; and 3-NH2, 5-I salicylic acid are suggested. The major dissociations of these compounds are by elimination of the elements of neutral molecules, e.g. water, methanol, ketene (from the acetylated compounds) carbon monoxide, nitric oxide and nitrogen dioxide, leading to (iodo) phenoxy and (iodo) quinone type ion structures. These ions further decompose to yield the corresponding substituted cyclopentadienyl and cyclopropylium ions.
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  • 84
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    Biological Mass Spectrometry 1 (1968), S. 263-271 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of 2- and 3-phenylthiophenes and their phenyl-d5 counterparts reveal that the thienyl ring is markedly more reactive than the phenyl ring under electron impact. In one process, that leading to loss of C2H2S, the atoms lost are apparently derived solely from the thienyl ring, quite probably from the original molecular configuration.
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  • 85
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The triphenylmethyl (trityl) moiety is frequently used for the protection of alcohols but the mass spectra of such trityl ethers have hitherto escaped scrutiny. It has now been found that triphenylmethyl derivatives of primary alcohols yield abundant molecular ions which permit the determination of the isotopic purity of the parent alcohol. Upon electron impact the triphenyl-methyl entity directs the fragmentation of trityl ethers as demonstrated by a detailed study of n-pentyl trityl ether and its deuterated analogs. Ions formed by migration of phenyl groups were observed in the mass spectra of the trityl ethers investigated as well as in the spectrum of triphenyl-methane itself.
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    Biological Mass Spectrometry 1 (1968), S. 231-250 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The different influence of functional groups on fragmentation reactions is demonstrated by the example of 17β-hydroxy-5α-androstanes.In 17β-hydroxy-5α-androstane the tendency of steroids to be cleaved by rupture of the C-13/C-17 bond under production of a charged centre at C-13 is only enhanced by the hydroxyl group. This influence of the hydroxyl group only predominates as long as substituents are absent which need less energy for ionization than is necessary to ionize the C-13/C-17 bond. Even the presence of a double bond may change the fragmentation pattern completely.If, however, an additional alkyl group is located at C-17, ionization occurs with high probability by elimination of an electron from the OH group connected to C-17. Therefore, other main degradation reactions occur than in molecular ions, having the charge located at C-13. In such compounds even the dominant influence of a conjugated system on the fragmentation reactions is considerably reduced. By etherfication of the hydroxyl group this effect is still very much increased.In the course of this investigation some not yet known degradation reactions, rather typical for the presence of certain groups in the steroid skeleton, were found. These are discussed briefly.
    Notes: AM Beispiel des 17β-Hydroxy-5α-androstans wird der unterschiedliche Einfluß funktioneller Gruppen auf die Bruchstückbildung von Steroiden studiert.Im 17β-Hydroxy-5α-androstan wird durch die Hydroxylgruppe lediglich die in Steroiden vorhandene eigung zur Spaltung der C-13/C-17 Bindung unter Ausbildung eines positiven Ladungszentrums an C-13 vertärkt. Dieser Einfluß der Hydroxylgruppe überwiegt aber nur, solange Substituenten fehlen, die zur Ionisation einen geringeren Energieaufwand benötigen, als zur Ionisation der C-13/C-17 Bindung erforderlich ist. Bereits bei Vorhandensein einer Doppelbindung kann sich das Spaltbild stark wandeln.Wenn sich aber in Stellung 17 noch eine zusätzliche Alkygruppe befindet, so erfolgt die Ionisation mit hoher Wahrscheinlichkeit durch Abspaltung eines Elektrons vom Hydroxylsauerstoff in Stellung 17. Es treten daher andere Hauptabbaureaktionen ein als in Molekülionen, die das Ladungszentrum am C-13 haben. In solchen Verbindungen ist selbst der dominierende Einfluß eines konjugierten Systems auf die Bruchstückbildung weitgehend eingeschränkt. Bei Verätherung der Hydroxylgruppe wird dieser Effekt potenziert.Im Zuge dieser UNtersuchungen wurden einige bisher noch nicht bekannte, für die Anwesenheit bestimmter Strukturelemente im Steroidskelett typische Abbaureaktionen aufgefunden, die ebenfalls kurz diskutiert werden.
    Additional Material: 18 Ill.
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  • 87
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 279-284 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of some δ-lactones substituted in various positions by methyl groups have been studied both by accurate mass measurements at high resulution and by deuterium labelling. The loss of carbon dioxide has been shown to be important only for a mono-substituted lactone. A fragmentation mode common to all the lactones studied is the elimination of the ring oxygen atom, plus the adjacent carbon atom with its substituents, as a neutral carbonyl molecule such as formaldehyde, acetaldehyde or acetone. Deuterium labelling has uncovered the existence of a rearrangement involving hydrogen transfer in an even-electron ion, and a mechanism involving a six-membered transition state is proposed for this. The bond fissions, common to all the lactones, by which the principal ions in the mass spectra arise, are summarised.
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  • 88
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 285-294 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of nineteen substituted benzothiazoles have been recorded and the identity of the various ions in the mass spectra has been established by high resulution (accurate) mass measurement. Deuterium labelling has been used to elucidate the fragmentation processes of these compounds. The parent compound of the series, benzothiazole, exhibits the loss of hydrogen cyanide and carbon monosulphide from the parent ion as the most important decomposition pathways. The hydrogen atom concerned in the loss of hydrogen cyanide is shown to originate from the 2-position of benzothiazole, while in 2-substituted benzothiazoles, different mechanisms are apparent for the loss of hydrogen cyanide, and these are clarified by deuterium labelling. Some substituted benzothiazoles can lose sulphur from their molecular ions, a process which does not occur in benzothiazole itself. The substituted benzothiazoles undergo many other types of fragmentations, in some cases retaining the substituent, and in other cases losing it prior to collapse of the thiazole ring.
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  • 89
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 315-322 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The mass spectra of 19 aromatic isocyanides are reported and discussed. The main feature of the fragmentation of these compounds is loss of HCN usually indicated by a metastable peak. Although this process is characteristic of the behaviour of aromatic isocyanides the extent to which it dominates the mass spectrum of any aromatic isocyanide is determined by the relative ease of cleavage of other bonds within the molecule. 2,4,6-d3-phenylisocyanide (Ib) loses predominantly DCN from the molecular ion while 2,4-d2-1-naphthylisocyanide (lIIb) eliminates HCN. It is therefore concluded that the loss of HCN from aromatic isocyanides is mainly a non-random process (no randomization prior to fragmentation).
    Notes: Die Massenspekren von 19 aromatischen Isocyaniden werden angegeben. Hauptmerkmal des Elektronenstoß-induzierten Zerfalls dieser Verbindungen ist der Verlust von HCN, der gewöhnlich von einem metastabilen Peak begleitet wird. Obsleich dieser Prozeß charakteristisch ist für das Verhalten von aromatischen Isocyaniden, tritt er mehr und mehr in den Hintergrrund, wenn andere leicht spaltbare Bindungen im Molekül vorhanden sind. 2,4,6-d3-Phenylisocyanid (Ib) spaltet aus dem Molekülion vorwiegend DCN ab, während 2,4,d2-1-Naphthyl-isocyanid (IIb) hingegen HCN eliminiert. Es wird deshalb angenommen, daß bei der Abspaltung von HCN aus aromatischen Isocyaniden der dazu benötigte Wasserstoff aus einer spezifischen Stellung des Benzolkerns kommt und keine statistische Verteilung der Wassertoff-Atome vor der Fragmentierung eintritt.
    Additional Material: 9 Ill.
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  • 90
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 910-912 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The loss of HCN and DCN from 2,4,6-d3-phenyl isocyanide is preceded by H/D randomization in the large majority of k-states which could be sampled in this study.
    Additional Material: 1 Ill.
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  • 91
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    Biological Mass Spectrometry 1 (1968), S. 918-918 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 92
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 323-329 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: It is shown that in porphin derivatives the McLafferty rearrangement occurs preferentially in even electron systems, in fact with high relative abundance starting from M2+, but less favorably in ions formed by elimination of a radical. Starting from this observation the formulation of a general scheme for the McLafferty rearrangement is attempted.
    Notes: Es wird gezeigt, daß in Porphin-Derivaten die McLafferty-Umlagerung bevorzugt in geradelektronischen Systemen abläuft. und zwar mit großer relative Häufigkeit ausgehend von M2+, jedoch weniger begünstigt in Ionen, die durch Radikalabspaltung entstanden sind. Von dieser Beobachtung ausgehend wird ein allgemeines Schema für die McLafferty-Umlagerung vorgeschlagen.
    Additional Material: 2 Ill.
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  • 93
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 94
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    Biological Mass Spectrometry 1 (1968), S. 343-343 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 95
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968), S. 531-536 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The p-fluoro labeling technique is used to demonstrate that the ions formed by the loss of CO from tetracyclones pass through a tetrahedral transition state or intermediate before they fragment.
    Additional Material: 3 Tab.
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  • 96
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    Biological Mass Spectrometry 1 (1968), S. 537-542 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contrary to previous suppositions, it appears that the produced by the loss of 2 CO from para-benzoquinones passes through the symmetry of not a substituted cyclobutadiene, but rather a substituted tetrahedrane, at least for inert R. The p-fluoro labeling technique is used to obtain this result.
    Additional Material: 2 Tab.
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  • 97
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    Biological Mass Spectrometry 1 (1968), S. 81-86 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cracking patterns of thirty-three fluorinated methanes, ethanes and propanes have been tabulated. For many of the compounds molecular ions were not observed. A comparison has been made of some of the halomethyl ion abundances with stabilization energies that have recently been derived from appearance potential measurements. Rearranged halomethyl ions occur frequently in the fluoroethane spectra. Their intensities often exceed those resulting from simple carbon bond rupture.
    Additional Material: 5 Tab.
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  • 98
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    Biological Mass Spectrometry 1 (1968), S. 71-80 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectra of certain deuteriated binuclear chromium complexes have been obtained which help to elucidate some of the fragmentation processes of the molecular ion.The effect of the relative strengths of the metal-ligand and metal nitrosyl bonds is also discussed.
    Additional Material: 12 Ill.
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  • 99
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1968) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 100
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to discuss hydrogen transfer in the skeletal fragmentation of thioethers on electron impact, mass spectra of a series of 2-n-alkylthio-5-aminothiazolo [5,4-d]pyrimidines have been determined. To aid the interpretation of the hydrogen migration, deuterium-labeled compounds which are substituted with deuterium in each position of 2-n-butylthio-5-aminothiazolo-pyrimidines were studied. By correlation of the spectra obtained from such labeled compounds, the initial hydrogen migration in the fragmentation to produce [M — SH], [MS — CH3] and m/e 184 ions is concluded to be as follows: migration of the α-hydrogen atom to the sulfur induces formation of the [M — SH] ion; migration of the β-hydrogen atom to the sulfur or nitrogen atom by a McLafferty rearrangement induces formation of the m/e 184 ion; and migration of γ-hydrogen atom to the sulfur induces formation of the [M — SCH3] ion.
    Additional Material: 2 Ill.
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