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  • 1965-1969  (107)
  • 1890-1899
  • 1870-1879
  • 1968  (107)
  • Analytical Chemistry and Spectroscopy  (92)
  • Cat  (15)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 127 (1968), S. 221-231 
    ISSN: 1432-0568
    Keywords: Marginal glia ; Superficial nerve cells ; Brain stem ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung An Paraffinschnitten durch perfusionsfixierte Gehirne von erwachsenen Katzen werden in der Glia marginalis des Hirnstamms unterschiedlich gebaute Bezirke beschrieben. Es wird gezeigt, daß über dem Nucleus paragigantocellularis und über dem Ncl. “z” swischen den Fasern der Glia marginalis Nervenzellen liegen. Über dem erstgenannten Kern stellen diese Zellen möglicherweise das morphologische Substrat der chemosensiblen Felder dar, die durch die physiologischen Untersuchungen von Loeschcke, Mitchell u.a. bekannt geworden sind.
    Notes: Summary In the marginal glia covering the brain stem of the cat, regional differences are described in paraffin sections of brains which had been fixed by perfusion of Bouin's fluid. It is shown that between the glia fibres covering the nucleus paragigantocellularis and the nucleus “z” there are nerve cells. It is suggested that in the region of the nucleus paragiganto-cellularis these cells are the morphological substrate of a chemosensible zone described in physiological experiments by Loeschcke, Mitchell and others.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 127 (1968), S. 138-144 
    ISSN: 1432-0568
    Keywords: Capillary density ; Postnatal development ; Corpus callosum ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung An Paraffinschnitten durch das Corpus callosum perfusionsfixierter Gehirne von 19 Katzen im Alter von einem Tag bis zu 2 1/2 Jahren wurde das Capillarvolumen bestimmt. Es beträgt bei der neugeborenen Katze 0,81 Vol.-%. In der 2. Lebenswoche beginnt eine Zunahme, die in der 5. Woche ein Maximum von 2,92 Vol.-% erreicht. Im Verlauf der 6. Woche setzt eine zunächst rasche, von der 7. Woche an aber nur noch langsam verlaufende Abnahme ein, bis bei einem Lebensalter von etwa 1 Jahr ein für das erwachsene Tier charakteristischer Wert um 1,5 Vol.-% erreicht wird. Die Abnahme des Capillarvolumens hängt mit der Markscheidenbildung und der dadurch bedingten Zunahme des Fasermaterials zusammen.
    Notes: Summary Postnatal changes of capillary density have been determined in paraffin sections through the corpus callosum of 19 cats. At birth the capillary density amounts to 0.81 vol.-%. In the 2nd week of postnatal life it begins to increase and reaches a maximum of 2.92 vol.-% in the 5th week. From the 6th week onwards there is an initially steep and later on less pronounced decrease until at an age of about 1 year a value of about 1.5 vol.-% is reached, which is maintained in adult life. — The decrease in the percentage of capillary volume seen after the 5th week is caused by the rapid increase in fibrous material due to myelination.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 5 (1968), S. 210-234 
    ISSN: 1432-1106
    Keywords: Sensorimotor cortex ; Pontine nuclei ; Somatotopical localization ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Small lesions (in some cases bilateral) were made in the cerebral primary sensorimotor region in altogether 21 adult cats and the ensuing degeneration in the pontine nuclei was studied with the silver impregnation methods of Nauta and Glees. Using thermocoagulation it was possible to obtain lesions restricted entirely to particular cortical regions (for example the “hindlimb region” in the posterior sigmoid gyrus). The main results are as follows: 1. All parts of the primary sensorimotor region send fibres to the pontine nuclei. The projections from the posterior part of the posterior sigmoid gyrus and the posterior part of the coronal gyrus are relatively scanty. 2. The cortical “motor” area (the anterior sigmoid gyrus and the anterior part of the coronal gyrus) and the “sensory” area (the posterior sigmoid gyrus and the posterior part of the coronal gyrus) do not project to identical pontine regions, although both projections are organized in principally the same way. 3. The “motor” and “sensory” areas both project in a somatotopical manner onto two longitudinally oriented sharply delimited columns. In both projections one column is located medial and one lateral to the longitudinal fibre bundles of the corticospinal and corticobulbar tracts. Within the medial columns the “hindlimb” is represented ventrally with “face” most dorsally, within the lateral columns the “hindlimb” is located most caudally, with “forelimb” and “face” successively more rostrally. 4. The present results are in agreement with physiological observations on the cerebrocerebellar relations, but show that the pontine projection from the primary sensorimotor cortex is organized in a more complex manner than hitherto assumed.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 5 (1968), S. 55-60 
    ISSN: 1432-1106
    Keywords: EEG frequency ; Regional cortical blood flow ; Isotope measurements ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The EEG frequency content in cats, anaesthetized by Nembutal and artificially ventilated, was altered by means of injections of either additional Nembutal or of Metrazol. The EEG in cerveau isolé preparations was also changed in the same way. The regional cortical blood flow was determined by means of the 85Krypton technique. A high correlation was found between the frequency content of the EEG, measured by means of manual frequency analysis, and the regional cortical blood flow. The cortical blood flow increased when the mean frequency increased, and vice versa. A similar correlation was found when the EEG mean frequency was changed by means of sensory stimulation.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 5 (1968), S. 61-71 
    ISSN: 1432-1106
    Keywords: EEG frequency ; Regional cortical blood flow ; Isotope measurements ; Effects of hypoxia ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. The relationship between cortical blood flow and the frequency content of the EEG was studied in a circumscribed area of the exposed cerebral cortex in cats under nitrous oxide-oxygen anaesthesia. Autoregulation of the cortical blood flow was also tested during step-changes of the arterial blood pressure. Observations were made before and after an episode of severe hypoxia. 2. An episode of systemic hypoxia disrupted the normal high correlation between cortical blood flow and EEG frequency content. In the post-hypoxic period cortical flows of up to about three times normal values were recorded together with brain swelling and a slow wave EEG. The hyperemia and swelling subsided during 1–2 h after the hypoxic episode, and were accompanied by partial or complete recovery of the EEG. In the post-hypoxic period a defective autoregulation of the cortical blood flow to changes in the systemic blood pressure was demonstrated. 3. The cerebral post-hypoxic state with hyperaemia, brain swelling, EEG depression, and loss of autoregulation of blood flow, is probably caused by an accumulation of anaerobic metabolites which lead to cerebral tissue acidosis.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 5 (1968), S. 326-340 
    ISSN: 1432-1106
    Keywords: Subcellular fractionation ; Parallel fiber axons ; Cerebellum ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Fractionation of the cat cerebellum has revealed that the parallel fibers of the cerebellar cortex break into two types of fragments which can be recognized in thin sections and in suspensions of negatively stained material. Fragmented material correlates well with electron micrographs of parallel fibers in situ. Parallel fiber axons and their bulbous presynaptic expansions sediment mainly into two subfractions. One unique layer consists of the intersynaptic tubular pieces of parallel fiber axons. Another layer is enriched in the synaptic portions which make contact with Purkinje spines. The possible contaminants of these fractions are discussed. These fractions may permit analysis of the chemical organization of conducting vis à vis synaptic membranes from a known anatomical source. This material was presented as a preliminary report at the Sixth Annual Meeting of the American Society for Cell Biology, November 1966, and is contained in J. Cell. Biol. 31, 52A, 1966.
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  • 7
    ISSN: 1432-1106
    Keywords: Cerebral cortex ; Thalamus ; Cat ; Nauta
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The corticothalamic projections from the gyrus proreus and the medial wall of the rostral hemisphere have been studied in the cat with the silver method of Nauta. The gyrus proreus projects upon the following nuclei (for abbreviations, see list on page 133), ipsilateral R, VA, VM, VL, MD, Pc, CL, CM, Pf, VPM, VPMpc. VPI and to the contralateral principal nucleus of the trigeminal nerve. The medial wall of the rostral hemisphere projects bilaterally upon R, VA, VM, VL, MD, Pc, CL, CM, Pf, VPM, VPMpc, VPI, VPL, the dorsal column nuclei and the principal nucleus of the trigeminal nerve. The ipsilateral thalamic projection is more abundant than the contralateral. The latter appears to increase in amount as the lesion is placed successively more ventrally on the medial wall of the rostral hemisphere. Some degenerating fibers cross in the corpus callosum and descend in the contralateral internal capsule but the majority cross in the dorsal part of the anterior commissure and reach the medial aspect of the anterior limb of the contralateral internal capsule. A somatotopical organization of the medial wall of the rostral hemisphere has been demonstrated. The rostrocaudal part projects upon the ipsilateral VPL lateralis (VPLl) and nucleus cuneatus and the contralateral nucleus gracilis and VPL medialis (VPLm). The caudal part of this cortical area sends fibers bilaterally to VPM, VPMpc, and the principal nucleus of the trigeminal nerve. The intermediate part, which also includes agranular cortex on the medial wall, projects upon ispsilateral VPLm and nucleus gracilis and upon contralateral VPLl and nucleus cuneatus. — The fibers to the ventro-basal complex, dorsal column nuclei and the principal nucleus of the trigeminal nerve are rather thick. The corticofugal fibers to the other thalamic nuclei are quite thin. — The findings are discussed in light of relevant anatomical and physiological observations in the literature and special emphasis has been laid on reported observations on the “supplementary motor” area.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 5 (1968), S. 153-172 
    ISSN: 1432-1106
    Keywords: SII ; Thalamus ; Cat ; Somatotopical localization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The corticothalamic projection from the anterior ectosylvian gyrus in the cat has been studied with the silver impregnation method of Nauta. The second somatosensory cortical area (SII) projects upon the ipsilateral nucleus ventralis posterolateralis (VPL), nucleus ventralis posteromedialis (VPM), the posterior thalamic region (PO) and to a slight extent upon the reticular nucleus of the thalamus (R), the centrum medianum (CM), the parvocellular part of VPM (VPMpc) and the nucleus ventralis posterior inferior (VPI). A somatotopical arrangement in the projection upon the ventro-basal (VB) complex has been demonstrated and a topical arrangement in the corticothalamic fibers from SII to PO is also evident. The transitional area between SII and the second auditory cortex sends fibers mainly to the entire magnocellular part of the medial geniculate body (MGmc) and to a lesser degree to the principal division of this nucleus (MGp). The corticofugal fibers from SII follow various and rather complicated circuitous routes before they end in the different thalamic nuclei. The experimental findings are discussed in the light of recent anatomical and physiological observations. It is shown that zones B and C of SII which have been shown by Carreras and Andersson (1963) to possess a large number of place and modality specific neurons project upon the VB-complex. On the other hand, zone A which contains a majority of place and modality unspecific neurons sends its fibers exclusively to PO. Finally the problem of thalamocortical projections to SII is briefly discussed.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 6 (1968), S. 234-246 
    ISSN: 1432-1106
    Keywords: Tactile discrimination ; Dorsal column-medial lemniscus ; Spino-cervico-thalamic tract ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The role of two spinal sensory pathways, the dorsal column (DC) pathway and the spino-cervico-thalamic tract (SCTT), involved in tactile discrimination was studied. Pour lesion groups of cats (DC lesion, SCTT lesion, combined DC and SCTT lesion, and sham-operated) were tested to discriminate various degrees of roughness. Animals with either the SCTT or the combined lesions performed at around 50–60% level under all the conditions tested. On the other hand, those with the DC lesion and sham-operations generally attained 80–100% level of performance. A difference between the DC group and sham-operated group was found in their rate of learning and ability for finer discrimination. These results are interpreted as an indication that a duplicity in transmission of tactile sensation exists, the DC pathway being more specific than the SCTT.
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  • 10
    ISSN: 1432-0533
    Keywords: Alumina Cream ; Intracerebral Injection ; Pathology of Growing Brain ; Myelination ; Demyelination ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Zum Studium der Reaktion des jugendlichen und erwachsenen Gehirnes auf einen chronischen Reiz wurden bei Katzen verschiedenen Lebensalters intracerebrale Injektionen von Aluminiumhydroxyd vorgenommen. Die Tiere wurden nach Überlebenszeiten von 7 Tagen, 40 Tagen und 3 Monaten durch Perfusion mit Bouinscher Lösung getötet. Die histologische Untersuchung der Gehirne ergab eine Reihe von Unterschieden, je nachdem ob die Injektion vor oder nach der Markscheidenbildung erfolgt war. Besonders auffällig war der Befund, daß in der noch unmyelinisierten weißen Substanz jugendlicher Tiere kein Hirnödem und keine Gliose auftritt. Obgleich durch fluorescenzmikroskopische Untersuchungen gezeigt werden konnte, daß das Aluminium von der Injektionsstelle aus weit in das umgebende Hirngewebe eindringt und dort über lange Zeit festgehalten wird, werden bei den jungen Tieren die Markscheiden später bis in die unmittelbare Umgebung des Herdes normal angelegt. Bei erwachsenen Tieren kam es dagegen in der Nachbarschaft des Herdes stets zu einem starkem Ödem der weißen Substanz, zum Zerfall der Markscheiden und zu einer ausgebreiteten Gliose. Weitere Unterschiede in der Reaktionsweise des Gehirnes jugendlicher und erwachsener Tiere, die den Cortex und insbesondere die marginale Gliafaserschicht betreffen, werden im einzelnen beschrieben und diskutiert.
    Notes: Summary In order to compare the reaction to chronic irritation of young and adult brain intracerebral injections of alumina cream were made in cats of various ages. The animals were killed by perfusion with Bouin's fluid after a survival time of 7 days, 40 days, and 3 months. Histological investigation revealed gross differences in the reaction according to whether the intracerebral injections had been made before or after myelination. Particularly striking was the finding that in the non-myelinated white matter of young animals there was no edema and no subsequent gliosis. Although alumina, as evidenced by fluorescence microscopy after staining with Morin, spreads into the tissue surrounding the focus, subsequent myelination appeared to be normal even in regions close to the site of injection. In contrast, injection into the brains of adult animals was followed by edema, widespread demyelination and gliosis of the white matter near the site of injection. Further differences between young and adult animals were found in the reaction of the grey matter and particularly of the marginal glia.
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  • 11
    ISSN: 1432-2013
    Keywords: Cat ; Electrophysiology ; Single Units ; Bulbar Trigeminal Nuclei ; Katze ; Elektrophysiologie ; Einzelneurone ; Bulbäre Trigeminuskerne
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung 1. Funktionelle Eigenschaften der excitatorischen Verbindungen von Cortex, Thalamus und Peripherie zu 438 Neuronen der bulbären Trigeminuskerne wurden untersucht. Es konnten Beziehungen zwischen den Latenzzeiten der Antworten auf ipsilaterale, periphere Einzelreize, contralaterale thalamische Einzel- und Serienreize (N. ventralis posteromedialis) und contralaterale corticale Einzel- und Serienreize (somatosensorisches Projektionsgebiet S I, S II) nachgewiesen werden. 2. Für die Gesamtheit der Neurone wurde mit zunehmender Latenzzeit der Entladung auf periphere Reize eine Zunahme der prozentualen Ansprechbarkeit und der Latenzzeit der Antwort auf zentrale Reize beobachtet. 3. Die Neurone, deren periphere, thalamische und corticale Antworten Reizfrequenzen von 50 Hz und mehr folgten, hatten im Mittel kürzere periphere Latenzzeiten als Neurone, die Reizfrequenzen von 50 Hz nicht folgten. 4. Bulbäre Neurone, die mit thalamischen Reizen antidrom erregt wurden (lemniscale Neurone), unterschieden sich im Mittel von den übrigen Neuronen durch kürzere Latenzzeiten für periphere und zentrale Reize. 5. Es wurden lemniscale Neurone beobachtet, die mit corticalen Reizen monosynaptisch erregt werden konnten. 6. Neurone mit kleinen peripheren rezeptiven Feldern hatten im Mittel kürzere Latenzzeiten auf periphere Reize als Neurone mit großen rezeptiven Feldern. 7. Die periphere Reizantwort von Neuronen konnte durch vorausgehende thalamische und corticale Reize gehemmt werden. Im Mittel wurde die Hemmung bei Neuronen mit Latenzzeiten auf periphere Reize häufiger beobachtet. 8. Mögliche Bahnen, die an der Übertragung thalamo-bulbärer Effekte beteiligt sind, wurden diskutiert und schematisch dargestellt. Die Ergebnisse wurden mit statistischen Methoden geprüft.
    Notes: Summary 1. Functional properties of excitatory connections from cortex, thalamus and periphery to a total of 438 trigeminal bulbar neurons of the cat have been investigated extracellularly. For the sample considered, correlations between latency of response to ipsilateral electrical single stimuli, contralateral electrical thalamic single and serial stimuli (N. ventralis posteromedialis) and also contralateral electrical cortical single and serial stimuli (somatosensory areas S I, S II) were established. 2. With increasing peripheral latency of response, the percentage of neurons responding to central stimulation increased as well. 3. Neurons following thalamic, cortical or peripheral stimulation frequencies of 50 cps or more showed in the average shorter latencies of response compared with neurons that could not be driven with 50 cps stimulation. 4. Bulbar neurons antidromically invaded by stimulation of the thalamus showed shorter latencies to peripheral, thalamic and cortical stimuli compared with other neurons. 5. Lemniscal neurons that could be activated monosynaptically by cortical stimulation have been observed. 6. Neurons with a small peripheral receptive field had in the average a shorter latency to peripheral stimuli than neurons with a large receptive field. 7. Responses to peripheral stimuli could be inhibited by preceding thalamic and cortical stimuli. 8. Possible pathways that are involved in transmission of thalamo-bulbar effects have been discussed and schematically represented. 9. All results have been examined by means of statistical methods.
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  • 12
    ISSN: 1432-2013
    Keywords: Hippocampus ; Corpus geniculatum laterale ; Katze ; Mikroelektrophorese ; Acetylcholin ; Hippocampus ; Lateral Geniculate Body ; Cat ; Microelectrophoresis ; Acetylcholine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary 1. Hippocampal and lateral geniculate neurones in anaesthetized cats (Chloralose-Urethane) were examined with multibarrelled microelectrodes, testing their responsiveness to microelectrophoretic application of acetylcholine and photic stimulation. 2. In the ventral hippocampus and in the lateral geniculate body 60% of all neurones responded to acetylcholine. 3. Hippocampal neurones were activated with relatively short delay, often less than 1 sec. By contrast, lateral geniculate neurones responded with a latency period of 2–12 sec. The recovery time after acetylcholine-microelectrophoresis was found to be 10–20 sec in both regions. 4. The response of hippocampal and lateral geniculate neurones to photic stimulation was enhanced by local application of acetylcholine; even during phenobarbital depression the photic responses were restored by acetylcholinemicroelectrophoresis.
    Notes: Zusammenfassung 1. Neurone im Gebiet des Hippocampus und des Corpus geniculatum laterale der mit Chloralose-Urethan narkotisierten Katze wurden mit mehrkanüligen Mikroelektroden auf ihre Ansprechbarkeit auf mikroelektrophoretisch appliziertes Acetylcholin und auf optische Reizung untersucht. 2. Im ventralen Hippocampus und im Corpus geniculatum laterale wurden 60% aller untersuchten Neurone durch Acetylcholin aktiviert. 3. Die Neurone des Hippocampus wurden nach relative kurzer Latenz, oft weniger als 1 sec, aktiviert. Neurone des Corpus geniculatum laterale dagegen zeigten eine Latenz von 2–12 sec. Die Zeit nach der Mikroelektrophorese bis zur Wiedererreichung der normalen Aktivität betrug 10–20 sec für beide Gebiete. 4. Die Acetylcholin-Mikroelektrophorese verstärkte die Reizantwort der Neurone des Hippocampus und des Corpus geniculatum laterale auf visuelle Reizung. Die nach Phenobarbital abgeschwächte Antwort auf visuelle Reizung wurde durch Acetylcholin-Mikroelektrophorese wieder verstärkt.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 4 (1968), S. 321-329 
    ISSN: 1432-1106
    Keywords: Temperature ; Interval histograms ; Optic nerve ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung In 13 Katzen wurde die Aktivität von 128 Einzelfasern des N. opticus bei Temperaturen zwischen 27 und 39° C abgeleitet und direkt einer Intervallanalyse zugeführt. Die Durchschnittsfrequenz sank mit abnehmender Temperatur von 56/sec bei 39–37° C auf 21/sec unter 29° C. Bei Temperaturen über 35° C wurden nur unimodale oder zweigipfelige Verteilungen mit gehäuften Mehrfachentladungen gefunden. Unter 35° C traten multimodale Intervallhistogramme und Übergangstypen auf, bei denen einer Verteilung mehrere Gipfel aufgesetzt erschienen. Unter 29° C wurden nur mehrgipfelige Verteilungen beobachtet. In der phasischen Reaktion der Neurone wurden mit der Temperaturabnahme Latenzen länger und Hemmungen stärker. Unter 30° C konnte der Reaktionstyp des Neurons oft nicht mehr erkannt werden. Das vermehrte Auftreten multimodaler Verteilungen bei niedrigen Temperaturen ließe sich durch Verminderung von Interaktionen in der Retina erklären. Die Anregung zu dieser Untersuchung wurde von Herrn Professor Dr. Hans Bornschein gegeben.
    Notes: Summary The activity of 128 single fibers of the optic nerve was recorded in 13 cats at temperatures between 27 and 39° C. Nonsequential interval histograms were computed on line. Decreasing temperature diminished the mean frequency of the fiber activity from 56/sec at 37–39° C to 21/sec below 29° C. Above 35° C the histograms were unimodal or bimodal, the first peak caused by repetitive discharges. Below 35° C multimodal histograms appeared; in some distributions several peaks were superimposed. At temperatures below 29° C only multimodal distributions were obtained. The phasic response of the neurons to light showed an increase of latency and of inhibition according to the decrease of temperature. Often the type of the response of the neuron could not be recognized below 30° C. During hypothermia interactions in the retina may be reduced and this may explain why multimodal distributions occur more frequently.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    European archives of psychiatry and clinical neuroscience 211 (1968), S. 43-62 
    ISSN: 1433-8491
    Keywords: Neuronal activity ; EEG-cortex ; Hypoglycemia ; Cat ; Neuronale Aktivität ; EEG-Cortex ; Hypoglykämie ; Katze
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung 1. An Katzen wurden EEG-Veränderungen durch Hypoglykämie hervorgerufen und mit den Aktivitätsveränderungen corticaler Neurone verglichen, wie sie sich bei intracellulären und „quasi-intracellulären“ Ableitungen darstellen. Es zeigte sich, daß pathologische EEG-Veränderungen erst bei niedrigen Blutzuckerwerten (zwischen 30 und 25 mg-%) auftreten und daß es erst bei Werten unter 10–15 mg-% zur elektrischen Stille kommt. 2. Während des flachen, desynchronisierten EEG des wachen Hirns vor Hypoglykämie lassen sich keine Beziehungen zwischen den kleinen EEG- und statistisch verteilten Zellpotentialen nachweisen. — Während der regelmäßigen 8–10/sec- Spindelgruppen, die bei tiefer Hypoglykämie häufig zu beobachten sind, findet sich eine enge Korrelation zwischen den einzelnen Oberflächen-negativen Spindelwellen und Zelldepolarisationen, die meist unterschwellig sind. 3. Bei den langsamen Wellen der δ-Frequenz finden sich ähnliche, aber weniger enge Korrelationen für die flachen, „monomorphen“ δ-Wellen. Andere Formen von langsamen Potentialkomplexen des Cortiocogramms, die im Tintenschreiber als „polymorphe“ δ-Wellen imponieren können, zeigen etwas andere, aber für den einzelnen Wellenkomplex jeweils konstante Beziehungen zur Zellaktivität. 4. Die steilen Wellen wurden unterteilt in primär positive und in primär negative bi- (oder auch tri-)phasische Potentiale. Die primäre Phase der primär-positiven steilen Potentiale ist im Durchschnitt kürzer (unter 20–40 msec) als die negative Phase der primär-negativen Phase (über 100 msec). Die meist überschwellige Zelldepolarisation, die in der Regel zu einer kurzen Gruppenentladung führt, fällt mit der primären Phase, also entweder der positiven oder der negativen zusammen. Die Phasenkoppelung, d. h. die „Synchronisation“ mit dem EEG-Potential, ist jedoch im Fall der primär-positiven Phase enger und die Dauer der Depolarisation kürzer als im Fall der primär-negativen steilen Potentiale. Diese Befunde werden als Hinweis auf eine stärkere Synchronisation der Aktivität der corticalen Nervenzellpopulation im Fall der primär-positiven steilen Potentiale gewertet. 5. Die verschieden engen Phasenkoppelungen und die je nach Steilheit der Wellen wechselnden Phasenbeziehungen zwischen Zellaktivierung und oberflächennegativen resp. -positiven Potentialen werden an Hand eines einfachen Modells der Elektrogenese von EEG-Potentialen erklärt, das den Synchronisationsgrad cortico-petaler und cortico-fugaler Faseraktivität sowie die Summation postsynaptischer Potentiale corticaler Neurone berücksichtigt.
    Notes: Summary 1. The EEG, recorded monopolarly from the pial surface, was investigated during insuline induced hypoglycemia in acute cats and compared with the activity of cortical cells recorded with intra or “quasi-intracellular” electrodes. 2. Pathological changes of the EEG were observed only when the blood glucose fell below 25–30 mg-%. Electrical silence was observed at blood glucose levels below 15–10 mg-%. 3. The essentially flat, “desynchronized” EEG of the awake animal before hypoglycemia did not show any relation between the small, irregular fast EEG- potentials and the statistically distributed cellular potentials. —During the regular 8–10/sec spindles (Fig. 3) a close correlation was found between the single surface- negative spindle waves and the mostly subthreshold compound cellular EPSP's. 4. Slow waves of δ-frequency showed similar but less close correlations, if the waves were of regular appearance comparable to “monomorphic” δ-waves (Fig.4A). Other forms of slow complex potentials (Fig.4B and C), which correspond to “polymorphic” δ-waves in an EEG-record (e.g. Fig.4C and Fig.2d) may show different relations between cellular and EEG-activity which were, however, consistent for each type of complex wave. 5. Sharp waves were divided into primary positive and primary negative bi- (or tri-)phasic potentials. The primary positive phase was always shorter (below 20–40 msec) than the primary negative phase (above 100 msec). The mostly suprathreshold cellular depolarization, which may lead to a short burst of discharge, coincided with the primary, i.e. either the primary positive or the primary negative phase (Fig. 7 shows records from the same cell and different EEG-phenomena). The phase coupling, i.e. the “synchronization” with the EEG-potential, is closer in the primary positive than the primary negative waves, and the duration of the cellular depolarization is also shorter in the former case (compare Fig.7B I–III with 7B IV). This can be interpreted as stronger synchronization of cellular activity during the short primary positive waves. 6. A causal relation between cortical neuronal activity and EEG-potentials is assumed. Differences in the closeness of phase coupling and the changing phase relation between cellular and EEG-activity according to the form and steepness of cortical EEG-potentials are explained by a simple model of electrogenesis of EEG-potentials, which takes in account the degree of synchronization of corticopetal and cortico-fugal fibre activity as well as the summation of postsynaptic potentials of cortical neurones.
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  • 15
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    Springer
    European archives of psychiatry and clinical neuroscience 211 (1968), S. 155-169 
    ISSN: 1433-8491
    Keywords: Sleep EEG ; Experimental Epilepsy ; Cat ; Schlaf-EEG ; Experimentelle Epilepsie ; Katze
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die Frage der Wacho- der Schlaf-Aktivierung der fokalen Epilepsien wird bei 20 epileptischen Katzen im chronischen Experiment untersucht (Kopeloff-Methode). Die Narben wurden im Nucleus amygdaloideus (Pars basolateralis), Hippocampus dorsalis, Formatio reticularis mesencephali, Isocortex gesetzt. Bei einer Untersuchungsdauer der einzelnen Tiere zwischen 3 und 60 Tagen, wurden insgesamt 442 Std in Polygraphie (EEG, EMG, Augenbewegungen) abgeleitet. Die Tiere zeigten innerhalb der ersten 7 Tage Krampfpotentiale im EEG und die meisten ab der 2. Woche Krampfanfälle. Bei Katzen mit subcorticalen Narben war keine Veränderung der Dauer, der Verteilung und der Organisation der einzelnen Schlafstadien nachweisbar. Die im Ruhe-EEG vorhandenen Paroxysmen wurden während des langsamen Schlafes nicht aktiviert und fokalisiert. Im paradoxen Schlaf waren die Krampfpotentiale völlig desaktiviert, es traten einzelne Spindeln auf. Die Tiere mit Narben im Isocortex zeigten im langsamen Schlaf seltene Paroxysmen. Während der häufigeren kurzen Phasen des paradoxen Schlafes war eine Fokalisierung der Spitzen im Bereich der Läsion nachweisbar, jedoch, keine Aktivierung. Bei allen Tieren war die ausgeprägteste Aktivierung der Krampfbereitschft stets in dem von uns als „Wach mit motorischer Inaktivität“ bezeichnete Phase zu bemerken. Daher wird angenommen, daß dieser Zustand bei der Katze mit dem Einschlafstadium des Menschen vergleichbar ist.
    Notes: Summary The activation of focal epileptic activities during wakefulness, slow and REM sleep was studied in chronic experiments in 20 epileptic cats (Kopeloff's method). The lesions were produced in the nucleus amygdaloideus (pars basolateralis), hippocampus dorsalis, formatio reticularis mesencephali and in the isocortex. Each animal was observed from between 3 to 60 days and a total of 442 hours of polygraphy (E.E.G., E.M.G, Eye movements) were recorded. Within the first 7 days all animals showed E.E.G paroxysms and most of them showed seizures from the beginning of the second week. In those cats with subcortical lesions there was no change detected in the duration, distribution and organisation of the different sleep phases. The paroxysmal E.E.G activity seen in the wakeful animal were not activated or focalised during slow-wave sleep; in REM sleep the paroxysms disappeared completely, only a few spindles were seen. Animals with lesions in the isocortex rarely showed paroxysms during the slow wave sleep. However, during REM sleep a clear focalisation was seen, although there was no additional activation in the area of the lesion. In all animals the most significant of the paroxysms was seen during a state which we should like to describe as; “Awake without any motor activity”. It is assumed that this state corresponds to the state of falling asleep in man.
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  • 16
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    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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  • 17
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    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.
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  • 18
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    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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  • 19
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    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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  • 20
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    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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  • 21
    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.
    Additional Material: 6 Ill.
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  • 22
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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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  • 23
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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
    Topics: Chemistry and Pharmacology
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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.
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  • 25
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    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.
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  • 26
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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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  • 27
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    Biological Mass Spectrometry 1 (1968), S. 483-485 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 28
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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.
    Additional Material: 5 Ill.
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  • 29
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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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  • 30
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    Biological Mass Spectrometry 1 (1968), S. 397-402 
    ISSN: 0030-493X
    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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  • 31
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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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  • 32
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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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  • 33
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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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  • 34
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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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  • 35
    ISSN: 0030-493X
    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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  • 36
    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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  • 37
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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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  • 38
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    Biological Mass Spectrometry 1 (1968), S. 907-909 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 39
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    Biological Mass Spectrometry 1 (1968), S. 913-914 
    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 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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  • 40
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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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  • 41
    ISSN: 0030-493X
    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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  • 42
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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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  • 43
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    Biological Mass Spectrometry 1 (1968), S. 527-530 
    ISSN: 0030-493X
    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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  • 44
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    Biological Mass Spectrometry 1 (1968), S. 519-525 
    ISSN: 0030-493X
    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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  • 45
    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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  • 46
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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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  • 47
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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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  • 48
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    Biological Mass Spectrometry 1 (1968), S. xi 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 49
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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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  • 50
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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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  • 51
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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
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  • 52
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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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  • 53
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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 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.
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  • 54
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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 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.
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  • 55
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    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.
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  • 56
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    Biological Mass Spectrometry 1 (1968), S. 918-918 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 57
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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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  • 58
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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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  • 59
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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 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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  • 60
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    Biological Mass Spectrometry 1 (1968), S. 31-46 
    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. 13-29 
    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 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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  • 62
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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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  • 63
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    Biological Mass Spectrometry 1 (1968), S. 215-229 
    ISSN: 0030-493X
    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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  • 64
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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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  • 65
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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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  • 66
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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.
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  • 67
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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.
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  • 68
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    Biological Mass Spectrometry 1 (1968) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 69
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The utility of benzoyl and pentadeuterobenzoyl derivatives of peptide methyl esters for mass spectrometric analysis was investigated. The mass spectra of the glu-his and the val-tyr-pro derivatives are discussed. Treatment of the peptide methyl esters with the mixed benzoic-ethyl-carbonic anhydride did in some cases lead to benzoyl derivatives as well as to ethoxycarbonyl derivatives.
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  • 70
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The utility of ethoxycarbonyl-peptide methyl esters for mass spectrometric analysis is described. The ethoxycarbonyl group has important advantages over other protecting groups which are in use. The derivatives have high intensity; this greatly facilitates the interpretation of the fragmentation pattern. The spentra of the methyl esters of the ethoxycarbonyl derivatives of pro-val, trp-gly, gly-ser, (cys)2, glutation (GSH), glu-his-phe, val-tyr-pro and val-lys-val-tyr-pro are given.
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  • 71
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    Biological Mass Spectrometry 1 (1968), S. 551-561 
    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 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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  • 72
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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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  • 73
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    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:
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  • 74
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    Biological Mass Spectrometry 1 (1968), S. 151-166 
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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 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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  • 75
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    Biological Mass Spectrometry 1 (1968) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 76
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    Biological Mass Spectrometry 1 (1968), S. 1-1 
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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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    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.
    Additional Material: 6 Ill.
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  • 78
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    Biological Mass Spectrometry 1 (1968), S. 47-60 
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    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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  • 79
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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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  • 80
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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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  • 81
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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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  • 82
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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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  • 83
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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.
    Additional Material: 10 Ill.
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  • 84
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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.
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    Biological Mass Spectrometry 1 (1968), S. 279-284 
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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 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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  • 86
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    Biological Mass Spectrometry 1 (1968), S. 285-294 
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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 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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  • 87
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    Biological Mass Spectrometry 1 (1968), S. 343-343 
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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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  • 88
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    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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  • 89
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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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    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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  • 91
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    Biological Mass Spectrometry 1 (1968), S. 503-517 
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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 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.
    Additional Material: 5 Ill.
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  • 92
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    Biological Mass Spectrometry 1 (1968), S. 531-536 
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    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.
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  • 93
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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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  • 94
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    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.
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  • 95
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    Biological Mass Spectrometry 1 (1968), S. 543-549 
    ISSN: 0030-493X
    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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  • 96
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    Biological Mass Spectrometry 1 (1968), S. 687-702 
    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 ten complexes derived from 3,3,3-trifluoroprop-1-yne, namely (CF3C≡CH)CO2(CO)6, (CF3C≡CH) [π—C5H5Ni]2, (CF3C≡CH)3Co2(CO)4, CF3CH2C[Co(CO)3]3, are discussed in terms of their structures. The major processes observed can be satisfactorily explained in terms of (i) loss of carbonyl groups, if present; (ii) loss of one fluorine atom from the parention (iii) elimination of neutral metal fluorides, with ligand transfer reactions in the case of the iron complexes; (iv) elimination of neutral fluorocarbon molecules.
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  • 97
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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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  • 98
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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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  • 99
    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 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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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
    Type of Medium: Electronic Resource
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