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  • 1965-1969  (353)
  • 1920-1924
  • Analytical Chemistry and Spectroscopy  (318)
  • Bone  (35)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 3 (1969), S. 308-317 
    ISSN: 1432-0827
    Keywords: Bone ; Enamel ; Hydroxyapatite ; X-ray Diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'objet de cette étude a été de déterminer l'effet du mode de préparation (par meulage) sur la largeur des raies de diffraction de l'émail. La préparation d'émail, par meulage, en utilisant divers procédés ainsi qu'une pièce à main dentaire conventionnelle provoque un élargissement des pics obtenus (002, 211, 200 et 202) lorsqu'on la compare avec de la poudre d'émail, obtenue par meulage à l'aide de billes. L'élargissement des raies n'est pas observé lorqu'un monocristal d'hydroxylapatite est meulé à l'aide d'un diamant fin. En général, l'élargissement est moins important, lorsque le meulage est effectué à l'aide de turbines dentaires. L'importance du meulage dépend de façon variable d'un ou plusieurs des facteurs suivants: rugosité des instruments coupants, vitesse de meulage, direction de meulage, et la présence ou l'absence d'eau. Le meulage prolongé par billes de l'émail provoque aussi un élargissement dans les mêmes conditions, cependant, l'os n'est pas endommagé. Ces résultats indiquent que l'émail est plus sensible que l'hydroxylapatite et l'os. L'élargissement de raies peut être dû soit à une déformation de la maille cristalline, soit à une diminution de taille des cristaux.
    Abstract: Zusammenfassung Es wurde eine Untersuchung durchgeführt, um den Einfluß der Probenvorbereitung (Zerreibungsmethode) auf die Breite des Linienprofil-Querschnittes von Zahnschmelz zu bestimmen. Gewinnung von Zahnschmelz mit den verschiedenen Schneidinstrumenten einer konventionellen Bohrmaschine verursachte eine Verbreiterung aller untersuchten Peaks (002, 211, 200 und 202) im Vergleich zum gleichen Schmelz, der mit dem Rosenbohrer zerrieben wurde. Eine Verbreiterung der Linie konnte nicht beobachtet werden, wenn ein einzelner Kristall von Hydroxyapatit mit einem ganz feinen Diamanten zerrieben wurde. Im allgemeinen war die Verbreiterung weniger ausgesprochen, wenn die hochtourige Bohrtechnik zur Anwendung kam. Das Ausmaß der Verbreiterung, das durch Zahnbohrer verursacht wurde, war abhängig von einem oder mehreren der folgenden Faktoren: Rauheit des Schneidinstrumentes, Zerreibungsgeschwindigkeit, Zerreibungsrichtung und das Vorhandensein oder Fehlen von Wasser. Verlängerte Zerreibung von Schmelz mit dem Rosenbohrer verursachte ebenfalls eine Verbreiterung. Unter identischen Bedingungen blieb der ausgeglühte Knochen jedoch unversehrt. Diese Beobachtungen zeigen, daß Schmelz für Zerreibungsschäden anfälliger ist, als Hydroxyapatitkristalle oder ausgeglühter Knochen. Die eigentliche Ursache der Linienverbreiterung kann entweder eine Schädigung infolge Distortion des Gitters oder eino Reduktion der Größe der individuellen Kristalle sein.
    Notes: Abstract A study was conducted to determine the effect of sample preparation (grinding method) upon breadth of the diffraction profile of enamel. Collecting enamel by grinding with various cuttin tools in the low-speed dental handpiece caused broadening of all peaks (002, 211, 300 and 202) examined, compared to ball, ground, counter-part enamel. Line broadening was not observed when a single crystal of mineral hydroxyapatite was ground with a very fine diamond. In general, broadening was less pronounced with the high-speed air turbine technique. The amount of broadening caused by dental burs depended upon one or more of the following factors: coarseness of cutting instrument, grinding speed, grinding direction, and the presence or absence of water. Prolonged ball grinding of enamel also caused broadening; under identical conditions, however, annealed bone remained undamaged. These findings indicate that enamel is more sensitive to grinding damage than the mineral hydroxyapatite crystal or annealed bone. The actual cause of line broadening may be either strain due to lattice distortions or a reduction in size of individual crystallites.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 162-173 
    ISSN: 1432-0827
    Keywords: Bone ; Resorption ; Parathyroid ; Bird
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'os médullaire des poules au moment de la ponte ainsi que l'os néoformé de coqs soumis à des substances oestrogéniques, ont été examinés par les méthodes de l'histologie, de l'histochimie, de la microradiographie et de l'alpharadiographie afin de comparer la résorption naturelle à celle produite par la parathormone. Chez les pondeuses, la résorption a été provoquée par la formation de la coquille; chez les coqs, elle s'est produite à la suite de la diminution du taux des oestrogènes. La résorption naturelle de l'os médullaire a été marquée par un accroissement de la basophilie, de l'azurophilie et de la metachromasie, par la diminution graduelle de la densité organique et minérale. Ces modifications ont été observées d'abord dans la portion distale de l'os médullaire; elles se sont progressivement propagées à la région sous corticale. L'extrait parathyroidien semble avoir favorisé tous ces phénomènes, en stimulant l'ostéolyse ostéocytaire et l'ostéoclasie. Il ne nous a pas été possible cependant de nous rendre compte si les ostéoclastes ne se sont attaqués qu'aux portions des travées déja modifiées par l'ostéolyse. Ces résultats concordent avec l'idée que la résorption normale de l'os médullaire de la poule au temps où la coquille de l'oeuf se dépose, est déclanchée par la parathormone. Il en est de même chez le coq à la suite du retrait des oestrogènes.
    Abstract: Zusammenfassung Die Substantia spongiosa der Femora von Legehennen und von Hähnen die mit Östrogen behandelt waren, wurde während spontaner und künstlicher, mit Extrakten von Epithelkörperchen induzierter, Resorption einer histologischen, histochemischen, alpharadiographischen und mikroröntgenographische Untersuchung unterworfen. Die natürliche Resorption wurde bei den Hennen durch die Eischalenproduktion und bei den Hähnen durch Östrogenentzug hervorgerufen. Die natürliche Resorption war durch erhöhte Basophilie, Azurphilie und Metachromasie, sowohl als auch durch verminderter alpharadiographischer und mikroröntgenographischer Dichte der Trabeculae der Substantia spongiosa charakterisiert. Diese Veränderungen wurden zuerst in den zentralen, dem Cavum medullare nächstgelegenen, Teilen der Spongiosa wahrgenommen. Später waren auch die peripheren Teile, mit geringerer Osteocytenkonzentration, betroffen. Diese Veränderungen konnten durch Gaben von Epithelkörperchenextrakten verstärkt werden. Die Resorption der Spongiosa wird durch osteocytische Osteolyse und Osteoklasie bewirkt. Es konnte aber nicht entschieden werden ob diese beiden Prozesse gleichzeitig stattfinden, oder ob die Osteoklasten die Trabeculae erst angreifen, nachdem sie bereits teilweise durch Osteolyse abgebaut worden sind. Diese Resultate stimmen mit der Hypothese überein, daß die natürliche Resorption von Spongiosa während der Eischalenproduktion bei Hennen und nach Entzug von Östrogen bei Hähnen, durch Epithelkörperchenhormonen bedingt ist.
    Notes: Abstract The medullary bone in the femora of laying hens and of oestrogen-treated cocks has been examined by histological, histochemical, alpharadiographic and microroentgenographic techniques while undergoing both natural resorption and resorption induced by injection of parathyroid extract. In the hens, natural resorption was brought about by egg-shell formation and in the cocks by withdrawal of oestrogen. Natural resorption was accompained by increasing basophilia, azurophilia and metachromasia and by decreasing alpharadiographic and microradiographic density of the trabeculae of the medullary bone. These changes were observed initially in the central region (towards the marrow cavity) and subsequently in the peripheral regions also, where the number of osteocytes per unit area of bone was less. Parathyroid extract enhanced all these effects. It appears that resorption of medullary bone was brought about by osteocytic osteolysis and by osteoclasis, but it was not possible to determine whether both processes occurred concurrently or whether the osteoclasts attacked the trabeculae only after they had been partially degraded by osteolysis. These results are consistent with the hypothesis that the natural resorption of medullary bone during egg-shell formation in hens and following the withdrawal of oestrogen in cocks is induced by parathyroid hormone.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 330-338 
    ISSN: 1432-0827
    Keywords: Collagen ; Electric current ; Electrolysis ; Precipitation ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'effet du courant électrique sur la collagène soluble, en solution dans l'acide acétique dilué, a été étudié pour des voltages, variant de O à 25 volts. Au-dessus de 2,6 volts, la vormation des bandes collagéniques (définies dans ce travail) parait inversement proportionelle, dans le temps, au voltage appliqué. La formation des bandes parait liée au processus d'électrolyse. Les auteurs démontrent que les pH élevés se situent au niveau de la cathode et qu'ils sont suffisants pour induire une précipitation du collagène. Les résultats antérieurs, publiés dans la littérature, décrivant l'action de courant électrique implanté, sont interpretés en fonction du mécanisme étudié au cours de ce travail.
    Abstract: Zusammenfassung Die Wirkung eines elektrischen Stromes auf verdünnte essigsaure Lösungen von löslichem Kollagen wurde bei Spannungen zwischen O und 25 Volt untersucht. Über 2,6 Volt wurde die Bildung von Kollagenbanden (in der Arbeit näher beschrieben) beobachtet, und zwar nach Zeiten, die der angewandten Spannung entgegengesetzt proportional verliefen. Die Bandenbildung wird dem Elektrolyseprozeß zugeschrieben. Wir konnten zeigen, daß sich die hohen pH-Werte rund um die Kathode entwickelten und daß diese genügen, um die Kollagenfällung zu veranlassen. Die Natur dieses Vorganges ist solcher Art, daß erin vivo als Antwort auf durch Stress verursachte Biopotentiale nicht vorkommen kann. Der hier beschriebene Mechanismus erlaubt es, Literaturangaben über den Effekt von implantierten Spannungsquellen zu interpretieren.
    Notes: Abstract The effect of electric current on dilute acetic acid solutions of soluble collagen has been studied for impressed voltages of from 0 to 25 volts. Above 2.6 volts the formation of collagen bands (herein defined) were observed at times inversely proportional to the applied voltage. Band formation is attributed to the process of electrolysis. It has been shown that the high pH values are generated in the area of the cathode, and that they are sufficient to induce collagen to precipitate. The nature of the process is such that it cannot occurin vivo as a response to stress induced biopotentials. Reports in the literature describing the effect of implanted voltage sources are interpreted in terms of the mechanism described here.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 1-12 
    ISSN: 1432-0827
    Keywords: Bone ; Resorption ; Osteocytes ; Lysosomes ; Collagenase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 39-47 
    ISSN: 1432-0827
    Keywords: Dehydroepiandrosterone ; Calcification ; Embryo ; Tissue Culture ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les modes d'utilisation de glucose, le contenu de calcium et d'hydroxyproline et la densité cellulaire du perioste de les os frontaux d'embryons de poulet de 12 et 13 jours de developpement, cultivés sur coagulum de plasma, se presentant différenment à chaque âge. Cultivés avec sulfate de déhydroèpiandrostérone en concentration 1 mM, les frontaux de 12 jours montrent un synthese augmentée du matrice osseuse, celle de 13 jours se calcifient à une vélocité significativement plus grande que celle des os contôles. Le degré de calcification au quatrième jour de culture measuré par la relation calcium/hydroxyproline, suit un fonction lineáire avec le logarithme des doses de sulfate de dehydroepiandrostérone employées (0.5, 1,0 et 2,0 mM). Les renseignements obtenus indiquent que les frontaux de 13 jours, cultivés “in vitro” constituent modeles experimentaux appropriés pour étudier l'effet des androgénes sur le tissue osseux.
    Abstract: Zusammenfassung Stirnbeine von Hühnerembryonen an ihrem 12. und 13. Entwicklungstag entnommen und in vitro kultiviert zeigen verschiedene Arten der Glucoseverwertung der Periostzellendichte, des Calcium- und Hydroxyprolingehaltes. Wird Dehydroepiandrosteronsulfat dem Medium in einer 1 mM-Konzentration zugegeben, so beteiligen sich die 12tägigen Stirnbeine vorwiegend an der Knochengewebesynthese, während die 13tägigen signifikant stärker verkalken als die Kontrollen. Gemessen an der Calcium/hydroxyprolin Ratio bildet die Verkalkung der 13tägigen Stirnbeine eine lineare Funktion mit den Logarithmen der verwendeten Dosen von Dehydroepiandrosteronsulfat (0,5, 1,0 und 2,0 mM). Das in vitro kultivierte 13tägige Stirnbein schein ein geeignetes Experimentiermodell zur Studie der Dehydroepiandrosteronsulfatwirkung auf das Knochengewebe zu sein, weil es das grundlegende Phänomen (erhöhte Verkalkung) wiedergibt, welches man auch bei mit Androgenen behandelten Menschen und Tieren beobachtet.
    Notes: Abstract Chick embryo frontal bones at 12 and 13 days of development cultivatedin vitro exhibit different patterns of glucose utilization, periosteal cellular density and calcium and hydroxyproline content. When dehydroepiandrosterone sulfate is added to the medium at a concentration 1 mM, 12-day frontals engage primarily in osteoid tissue synthesis while 13-day frontals calcify at a significantly greater rate than controls. Measured with the ratio calcium/hydroxyproline, the calcification of 13-day frontals follows a linear function with the logarithm of the doses of dehydroepiandrosterone sulfate employed (0.5, 1.0 and 2.0 mM). The 13-day frontal bone cultivatedin vitro seems to be an adequate experimental model for the study of the effects of dehydroepiandrosterone sulfate on bone tissue because it reproduces the basic phenomenon (increased calcification) observed in man and animals treated with androgens.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 94-100 
    ISSN: 1432-0827
    Keywords: Acid ; Base equilibrium ; Acidosis ; Bone ; Resorption ; Metabolism ; Osteoporosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'administration chronique de chlorure d ammonium à des rats adultes normaux, soumis à un régime contenant un taux approprié de vitamine D, provoque une ostéoporose. Celle-ci est provoquée par une perte de substance d'os et de minéral osseux, associée à l'augmentation de la résorption osseuse.
    Abstract: Zusammenfassung Chronische Verabreichung von Ammoniumchlorid an normale ausgewachsene männliche Ratten, die eine entsprechende Vitamin-D-haltige Diät erhalten, verursacht die Entwicklung einer Osteoporose. Die Osteoporose entsteht auf Grund eines Verlustes von Knochensubstanz und Knochenmineral, in Begleitung einer erhöhten Knochenresorption.
    Notes: Abstract Excessive administration of ammonium chloride to normal adult male rats receiving a diet adequate in vitamin D caused the development of osteoporosis. The osteoporosis was due to loss of bone substance and bone mineral associated with increased bone resorption.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 174-179 
    ISSN: 1432-0827
    Keywords: Calcium ; Strontium ; Bone ; Mineral
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé La proportion Sr/Ca dans l'os est à peu près la même que dans le sérum tandis que les poudres d'hydroxyapatite suspendues dans des solution physiologiques font une distinction contre le strontium. On trouva que la proportion Sr/Ca des fractions de différentes densités d'os compact de tibia de rat en forme de poudre augmentait avec augmentation de la densité jusqu'à une valeur un peu supérieure à celle observée dans le sérum. L'explication pourrait être qu'une barrière cellulaire ôte le calcium par préférence au strontium du fluide d'os ou bien qu'une accentuation précoce de la proportion Sr/Ca dans l'os se réfléchit dans les fractions de densité supérieure.
    Abstract: Zusammenfassung Das Verhältnis Sr/Ca im Knochen ist annähernd dasselbe wie es im Serum vorliegt, während in einer physiologischen Lösung von pulverisiertem Hydroxyapatit das Sr zugunsten des Ca benachteiligt wird. Es wurde festgestellt, daß das Sr/Ca-Verhältnis von Fraktionen verschiedener Dichte von pulverisierten Rattentibiae mit zunehmender Dichte anstieg, und zwar bis zu einem Wert, der etwas höher lag als der im Serum beobachtete. Dies ließe sich so erklären, daß eine Zellbarriere beim Entzug aus der Knochenflüssigkeit Ca dem Sr vorzieht; oder aber daß sich eine frühzeitige Betonung des für den Knochen typischen Sr/Ca-Verhältnisses in den Fraktionen höherer Dichte widerspiegelt.
    Notes: Abstract The Sr/Ca ration in bone is approximately the same as in serum, whereas hydroxyapatite powders suspended in physiological solutions discriminate against strontium. It was found that the Sr/Ca ratio of various density fractions of powdered compact bone of rat tibia increased with increasing density to a value slightly higher than that observed in the serum. The explanation could be that a cellular barrier removes calcium preferentially to strontium from the bone fluid, or that early accentuation of the bone Sr/Ca ration is reflected in the higher density fractions.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 180-184 
    ISSN: 1432-0827
    Keywords: Strontium ; Calcium ; Bone ; Shell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des poules ont été nourries avec une alimentation riche en strontium stable. Des concentrations de strontium de 3000 p.p. m. à 50000 p.p.m. montre une augmentation nette en strontium du tibia, alors que le contenu en calcium n'est pas modifié. Les concentrations en calcium sérique diminue, lorsque le strontium alimentaire augmente. Le calcium des coquilles d'oeufs diminue progressivement avec l'augmentation du strontium alimentaire, alors que le contenu en strontium des coquilles présente une augmentation correspondante. Des analyses de diffraction par rayons X des os et des coquilles ne permettent pas de déterminer sous quelle forme le strontium est déposé.
    Abstract: Zusammenfassung Die Resultate einer Verfütterung von hohen stabilen Strontiumdosen an Hühnern werden erläutert. Strontiumzusätze zur Nahrung in der Höhe von 3000–50000 p.p.m. führten zu einer signifikanten Zunahme des Strontiumgehaltes der Tibia und verursachten keine wesentlichen Änderungen des Calciumgehaltes. Die Calciumkonzentration im Plasma verminderte sich, wenn der Nahrung ansteigende Strontiummengen zugegeben wurden. Mit zunehmendem Strontiumzusatz zur Nahrung zeigte der Calciumgehalt der Eischale eine fortlaufende Abnahme, während sich der Strontiumgehalt entsprechend erhöhte. Durch Röntgendiffraktionsanalysen der stark Strontium-haltigen Knochen und Eischalen konnte nicht festgestellt werden, in welcher Form das Strontium abgelagert wurde.
    Notes: Abstract The results of feeding high dietary levels of stable strontium to hens are reported. Dietary levels of strontium from 3,000 p.p.m. to 50,000 p.p.m. showed a significant increase in strontium content of the tibia bone and essentially no change in the calcium content. Plasma calcium concentration was shown to decrease with increasing dietary strontium treatment. Egg shell calcium showed a progressive decrease with increasing dietary strontium treatment, whereas the strontium content has a corresponding increase. X-ray diffraction analyses of bones and shells containing large amounts of strontium were unsuccessful in evaluating the from in which strontium was deposited.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 202-209 
    ISSN: 1432-0827
    Keywords: Bone ; Radiocalcium ; Ascorbic acid ; Scintillimetry ; Radiocarbon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les auteurs on décrit des méthodes pour la détermination de45Ca plus L-1-14C acide asorbique dans les os d'animaux aprés administration des deux isotopes. Calcium et acide asorbique ont été extraits totalement par l'acide trichloracétique a 6% des os a l'état frais en évitant de détruire l'acide asorbique. La détermination chimique du calcium et de l'acide asorbique selon les méthodes classique a été faite dans des portions de l'échantillon. La détermination de la radioactivité du calcium et de l'acide asorbique a été faite ensuite dans des portions du même échantillon. Du Triton a servi pour le scintillant liquide dans le compteur de scintillation liquide. Un procédé de détermination des deux isotopes dans le meme echantillon a été décrit. Différents critéres on été appliques a chacque étape afin d'établir la validité et les limites d'application de la méthode.
    Abstract: Zusammenfassung Eine Methode ist beschrieben, die die quantitative und radioaktive Bestimmung von45Ca und L-[-L14C] Ascorbinsäure in Knochen von Tieren, denen die beiden Isotopen verabreicht worden sind, erlaubt. Calcium und Ascorbinsäure werden quantitativ mit 6% Trichloressigsäure ausgezogen, wobei die Ascorbinsäure erhalten bleibt. Quantitative Analysen für Calcium und Ascorbinsäure werden nach bekannten Methoden in einem Teil des Extraktes bestimmt und die Bestimmung der Radioaktivität in einem anderen Anteil mit Hilfe eines Flüssigkeits-Szintillations-Zählers durchgeführt. Dem flüssigen Szintillanten wird Triton zugesetzt. Diese Versuchsanordnung ermöglicht außerdem die gleichzeitige Bestimmung der beiden Isotopen im Knochen-Extrakt. Die Methode wurde sorgfältig auf ihre Verwendbarkeit ausgewertet.
    Notes: Abstract Methods were developed for the determination of45Ca plus L-[1-14C] asorbic acid in bones of animals following administration of both isotopes. Asorbic acid and calcium were extracted quantitatively with 6% trichloracetic acid from fresh bone under such mild conditions that asorbic acid was not destroyed. The chemical determinations of calcium and ascorbic acid according to standard procedures were performed in aliquots of the same extract. The determination of the radioactivity of calcium and ascorbic acid were then carried out in aliquots of the same extract. A Triton-containing liquid scintillation fluid was employed for the radioassay of45Ca and L-[1-14C] ascorbic acid in the liquid scintillation spectrometer. A procedure allowing the determination of both isotopes in the same extract is described. A number of criteria were applied to each step, in order to determine the validity and limitations of the procedure.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 291-304 
    ISSN: 1432-0827
    Keywords: Bone ; Fluorescence ; Resorption ; Deposition ; Calcium ; Microradiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Divers agents chimiques, colorés, fluorescents et se localisant dans les os, à savoir la tétracycline, l'alazazine rouge S et le DCAF, ont été administré en série à des rats sevrés et on a mesuré le taux de la formation et de la résorption osseuse sur les coupes transversales du tiers supérieur de la diaphyse. Ici la formation osseuse périostale s'effectue progressivement avec peu de changement endostéal. Avec alimentation carnée, la croissance des rats est significativement restreinte pendant la première semaine, mais se rétablit ensuite. Bien qu'il y ait croissance des os, ceux-ci ne se minéralisent pas normalement et ils deviennent rapidement fragiles et amincis. La résorption osseuse est lente d'abord, puis s'accelère pendant 2–3 semaines pour atteindre un taux de 15μ par jour, après quoi elle se ralentit de nouveau. Bien que le taux de formation osseuse soit réduit, en comparaison avec celui des os normaux, la résorption s'effectue environ deux à trois fois plus rapidement que la croissance osseuse. Des études microradiographiques sur des rats à régime carné mais carencés en calcium ont permis la constatation suivante: tandis que la résorption s'effectue à la marge endostéale et que la formation osseuse a lieu sur l'aspect périostéal, la matière osseuse nouvellement formée est moins calcifiéc que chez les témoins.
    Abstract: Zusammenfassung Einige farbige, fluoreszierende, knochensuchende Chemikalien, z. B. Tetracyclin, Alazarin-Rot S und CDAF, wurden nacheinander an entwöhnten Ratten verabreicht, worauf man die Knochenbildungs- und Knochenresorptionswerte an hartgeschliffenen Schnitten des oberen Drittels der Diaphyse gemessen hat. Hier findet fortschreitend periostale Knochenbildung statt, mit geringer Veränderung des Endosteums. Bei Fleischdiät wird das Körperwachstum während der ersten Woche erheblich beschränkt; danach aber normalisiert es sich wieder. Obwohl die Knochen noch wachsen, zeigen sie keine normale Mineralisierung und werden schnell zerbrechlich und dünn. Die Knochenresorption ist anfangs langsam, dann beschleunigt sie sich während einer Zeitspanne von 2–3 Wochen bis auf 15 μ pro Tag, um sich dann wieder zu verlangsamen. Während die Knochenbildungsgeschwindigkeit relativ zum Normalwert heruntergesetzt wird, verläuft die Resorption ungefähr 2–3mal so schnell wie die Knochenbildung. Mikroradiographische Untersuchungen an mit Fleisch ernährten Ca-armen Ratten haben bestätigt, daß während die Resorption am Endosteumrande stattfindet und sich die Knochenbildung an der Periostenfläche fortsetzt, die neugebildete Knochensubstanz weniger kalzifiziert ist, als die der Kontrolltiere.
    Notes: Abstract Different coloured, fluorescent bone-seeking chemicals, viz., tetracycline, Alizarin Red S, and DCAF, have been administered sequentially to weanling rats and the rate of formation and resorption of bone measured from hard-ground cross sections of the upper third of the diaphysis of the femur. On a meat diet, bodily growth is significantly restricted for the first week and then recovery occurs. While bones grow they fail to mineralize normally and rapidly become fragile and rarefied. Resorption of bone is at first slow, then accelerates for a period of 2–3 weeks to about 15μ/day and then slows again. While the rate of bone formation is reduced relative to normal bone, resorption proceeds at approximately two to three times the rate of bone growth. Microradiographic studies confirm tht while resorption occurs on the endosteal margin and formation proceeds on the periosteal aspect of meat fed Ca-deficient rats, new bone is less calcified than that in control animals.
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  • 11
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    Calcified tissue international 4 (1969), S. 136-146 
    ISSN: 1432-0827
    Keywords: Bone ; Calcification ; Osteoblasts ; Osteoclasts ; Poultry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'activité des cellules osseuses et la composition du fémur de pondeuses furent examinées pendant sept jours de déficience calcique (diète contenant 0,13% de calcium) et sept jours de réplétion (diète contenant 3,2% de calcium). Du point de vue histologique, seul l'os cortical donnait des signes nets de résorption et d'activité ostéoclastique. Le nombre d'ostéoclastes dans l'os médullaire différait peu des valuers témoin pendant les périodes de déficience et de réplétion subséquente, sauf pour une augmentation significative au premier jour de déplétion. L'effect histologique le plus important dans l'os médullaire était une augmentation marquée en nombre d'ostéoblastes aux troisième, cinquième, et un peu moins au septième jours de déplétion. Le nombre d'ostéoblastes était en corrélation positive avec la teneur de l'os médullaire en ostéoide et négative avec son degré de calcification. L'activité de l'os médullaire en phosphatase alcaline augmentait avec la longueur de la déficience calcique. Un jour après le retour des pondeuses à une diète contenant 3,2% de calcium, la calcification de l'os médullaire avait augmenté de façon significative, le nombre d'ostéoblastes avait diminué au niveau ou au-dessous du niveau de contrôle et l'activité de la phosphatase alcaline avait baissé considérablement. L'importance de ces résultats est discutée par rapport au controle des populations des cellules dan l'os et au rôle de l'os médullaire.
    Abstract: Zusammenfassung Die Zahl der Knochenzellen und die Zusammensetzung des Femurs von Legehennen wurden während einer siebentägigen Calciumentzugsperiode (Calciumgehalt des Futters 0,13%) und einer siebentägigen Ersatzperiode (Calciumgehalt des Futters 3,2%) untersucht. Histologisch zeigte nur die Cortex eindeutige Knochenresorption und osteoklastische Aktivität. Abgesehen von einer signifikanten Zunahme am 1. Tag des Calciumentzuges, variierte die Zahl der Osteoklasten im Markknochen sowohl während der Entzugs- als auch während der nachfolgenden Ersatzperiode wenig. Die wichtigste histologische Änderung im Markknochen bestand in einer starken Zunahme in der Zahl der Osteoblasten am 3., 5. und etwas weniger am 7. Tag der Entzugsperiode. Die Zahl der Osteoblasten zeigte eine positive Korrelation mit dem Osteoidgehalt des Markknochens und eine negative mit dem Grade seiner Verkalkung. Die Aktivität der alkalischen Phosphatase im Markknochen war desto größer je länger den Hennen die calciumarme Ration verfüttert worden war. Die Wiederverabreichung der Ration, welche 3,2% Calcium enthielt, verursachte innerhalb eines Tages eine signifikante Zunahme in der Verkalkung des Markknochens, ein Absinken der Osteoblastzahl auf die Kontrollwerte oder unter sie und eine drastische Verringerung der alkalischen Phosphataseaktivität. Die Bedeutung dieser Ergebnisse in bezug auf die Kontrolle des Knochenzellenbestandes und auf die Funktion des Markknochens wird diskutiert.
    Notes: Abstract Bone cell activity and the composition of the femur of laying hens were studied during 7 days of calcium depletion on a 0.13% calcium diet and 7 days of calcium repletion on a 3.2% calcium diet. Histologically, only cortical bone showed clear signs of bone resorption and osteoclastic activity during the depletion period. The number of osteoclasts in medullary bone varied little from control values throughout both calcium depletion and repletion, except for a significant increase on the first day of depletion. The major histologicalchange in medullary bone was a marked increase in the number of osteoblasts on the third, fifth and, to a lesser extent, seventh, day of depletion. The number of osteoblasts in medullary bone was positively correlated with its osteoid content and negatively correlated with its degree of calcification. Alkaline phosphatase activity of medullary bone increased with the time the hens had been on the calcium-deficient diet. Returning the hens to the 3.2% calcium ration caused, within one day, a significant increase in medullary bone calcification, a decrease of osteoblast numbers to, or below, control levels, and a drastic reduction in alkaline phosphatase activity of medullary bone. The significance of these findings in relation to the control of bone cell populations and the functions of medullary bone is discussed.
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  • 12
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    Calcified tissue international 4 (1969), S. 339-349 
    ISSN: 1432-0827
    Keywords: Bone ; Resorption ; Calcitonin ; Organ culture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une méthode quantitative pour étudier les effets précoces des hormones et autres agents sur la mobilisation du calcium osseux a été mise au point. Des moitiés de calottes craniennes de souris de 6 jours, ayant reçu du45Ca quatre jours auparavant, sont explantéesin vitro et placées dans des récipients séparés, en milieu liquide; une moitié sert de témoin, l'autre moitié est utilisée pour l'expérimentation. Ce mode d'action dans le temps, de chaque produit testé, est déterminé en prélevant aseptiquement de petits échantillons dans le milieu et en dosant l'isotope. L'hormone parathyroidienne et la vitamine A provoquent une résorption osseuse étendue ainsi qu'un passage augmenté du45Ca des os traités dans le milieu, au bout de 2 heures, si on les compare aux témoins. La calcitonine inhibe rapidement la mobilisation du45Ca des os résorbés: l'intervalle de temps est similaire à celui obtenuin vivo en abaissant le calcium sérique. Nos résultats indiquent que les agents, qui induisent la résorption osseuse, augmentent à la fois le nombre des ostéoclastes et l'efficacité des cellules existantes, en ce qui concerne la mobilisation du calcium. La calcitonine inhibe la libération du45Ca des explants vivants, maintenus dans un milieu contrôle. Cette réduction est attribuée à la suppression de la résorption endogène, en cours au moment de la transplantation: un échange isotopique est toujours observé, comme au niveau des explants sur vivants.
    Abstract: Zusammenfassung Eine quantitative Methode zur Bestimmung der Früheffekte von Hormonen oder andern Wirkstoffen auf die Wanderung von Calcium in den oder aus dem Knochen wurde entwickelt. Calvarien-Hälften von 6 Tagen alten, 4 Tage früher mit45Ca markierten Mäusen werden explantiert und in getrennten Schalen mit flüssiger Nährlösungin vitro belassen. Die eine Hälfte dient als Kontrolle, die andere wird für das Experiment eingesetzt. Anhand kleiner Proben, die den Medien aseptisch entnommen und auf ihren Isotopengehalt geprüft werden, kann die Wirkung der verschiedenen Agentien im Verlaufe der Zeit beobachtet werden. Sowohl Parahormon als auch Vitamin A verursachen eine ausgedehnte Knochenresorption und es wurde, im Vergleich zu den Kontrollen, innerhalb von 2 Std eine gesteigerte Abgabe von45Ca aus den behandelten Knochen in das Medium nachgewiesen, Die Freisetzung von45Ca aus resorbierenden Knochen wird durch Calcitonin rasch inhibiert. Wirkungsweise und Verlauf bestehen, wiein vivo, in einer Senkung des Serum-Calciums. Unsere Resultate zeigen, daß Wirkstoffe, welche eine Knochenresorption veranlassen, sowohl die Zahl der polynucleären Osteoklasten ansteigen lassen als auch die vorhandenen Zellen zur vermehrten Calcium-Mobilisation anregen. Calcitonin dagegen verhindert die Bildung neuer, polynucleärer Osteoklasten wie auch die Mobilisation von Knochenmineral durch die vorhandenen Osteoklasten. Calcitonin wirkt hemmend auf die Abgabe von45Ca von lebenden Explantaten, die in Kontrollmedium kultiviert werden. Diese Abnahme wird der Unterdrückung der endogenen Resorption zugeschrieben, welche im Moment der Knochenexplantation im Gange ist; der Austausch des Isotopes findet weiterhin statt, wie dies bei einem toten Explantat der Fall ist.
    Notes: Abstract A sensitive method has been developed for studying the early effects of hormones and other agents on the movement of calcium into and out of bone. Half-calvariae from 6-day-old mice that have been pulsed four days previously with45Ca, are explanted into separate dishes of liquid medium and maintainedin vitro; one half serves as control and the other for experimentation. The time course of action of any agent is followed by removing small samples aseptically from the media and analysing for isotope. Both parathyroid hormone and vitamin A cause extensive bone resorption, and as compared with controls an increased release of45Ca from the treated bones into the medium can be detected within 2 hours. Calcitonin rapidly inhibits the release of45Ca from resorbing bones; the time course is similar to that for its actionin vivo in lowering serum calcium. Our results indicate that agents that induce bone resorption increase both the number of multinucleate osteoclasts and the effectiveness of the existing cells in mobilising calcium. Calcitonin prevents the formation of new multinucleate osteoclasts, and also prevents existing osteoclasts from mobilising bone mineral. Calcitonin inhibits the release of45Ca from living explants maintained in control medium. This reduction is attributed to the suppression of the endogenous resorption that is in progress when the bones are explanted; exchange of isotope still occurs, as in a dead explant.
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  • 13
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    Calcified tissue international 4 (1969), S. 350-358 
    ISSN: 1432-0827
    Keywords: Bone ; Calcitonin ; Resorption ; Species ; Discrimination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une méthode quantitativein vitro est utilisée pour étudier l'efficacité relative des préparations de calcitonine, provenant de diverses espèces. La méthode est basée sur le fait que la calcitonine inhibe de façon nette la libération de45Ca de moitiés de calottes craniennes de souris, âgées de 6 jours, ayant été marquées auparavant; cet effect est lié à la suppression de la résorption endogène, qui se déroule, lorsque les os sont explantés et qui se continuein vitro en l'absence de calcitonine. Des différences nettes de l'effect d'inhibition des préparations de calcitonine ont été trouvées, qu'elles proviennent de corps ultimobranchiaux ou de thyroides de mammifères. La calcitonine humaine et la calcitonine porcine, standard A, se comportent de façon identique et sont environ dix fois plus actifs que la calcitonine porcinek standard B, en se basant sur les critéres unitaires utilisés au cours de cette étude chez le rat. Les calcitonines de corps ultimobranchiaux sont plus efficaces à doses faibles, pendant des périodes plus longues, que les préparations thyroidiennes et elles sont au moins dix fois plus efficaces que la calcitonine porcine standard A et cent fois plus actives que la calcitonine porcine standard B. Les explants traités par la calcitonine libère l'isotope dans le milieu d'une manière identique à celle de l'os mort, tant que la calcitonine reste active: pour la calcitonine de saumon, on observe pendant 20 heures un échange d'isotope entre l'os vivant, traité avec ce produit et le calcium du milieu, ainsi que cela se produit pour des fragments d'os congelé. Ces résultats sont utiles pour des études quantitatives, devant déterminer le mode d'action d'autres produits influençant la résorption et l'apposition osseuse. L'adjonction de calcitonine permet, en effet, de mesurer l'échange d'isotope libéré de l'os, ainsi traité à tous les stades, sans tuer les tissus ou sans avoir recours à des inhibiteurs spécifiques du métabolisme.
    Abstract: Zusammenfassung Ein quantitativerin vitro-Versuch wurde angewandt, um die relative Wirksamkeit von Calcitonin-Präparaten aus verschiedenen Spezies zu untersuchen. Der Versuch beruht auf der Feststellung, daß Calcitonin einen ausgeprägten Hemmeffekt auf die Freisetzung von45Ca aus markierten Calvarien-Hälften von 6tägigen Mäusen hat. Dieser Effekt kommt wegen der Unterdrückung der endogenen Resorption zustande, die im Moment der Knochenexplantation im Gange ist, undin vitrobei Abwesenheit von Calcitonin weiter fortschreitet. Auffallende Unterschiede des Hemmeffektes konnten bei Calcitonin-Präparaten sowohl von Ultimobranchialkörpern als auch von Säuger-Thyreoideae festgestellt werden. Menschliches Calcitonin sowie Standard A Schweine-Calcitonin verhalten sich gleich und sind ungefähr 10mal wirksamer als Standard B Schweine-Calcitonin, ausgedrückt in Einheiten bezogen auf den Rattenversuch. Die von Ultimobranchialkörpern stammenden Calcitonin-Präparate sind wirksamer in niedrigerer Dosierung und während einer längeren Zeitspanne als die Thyreoidea-Präparate. Sie wirken zudem mindestens 10mal stärker als Standard A Schweine-Calcitonin und 100mal stärker als Standard B Schweine-Calcitonin. Explantate, welche mit Calcitonin behandelt wurden, geben das Isotop auf die gleiche Weise wie totes Knochengewebe in das Medium ab, solange das Calcitonin wirksam ist. Für Calcitonin vom Lachs besteht eine Zeitpsanne von 20 Std, während welcher die lebenden, mit diesem Präparat behandelten Knochen das Isotop mit dem Calcium des Medium austauschen, in gleicher Weise wie durch Einfrieren und Auftauen getöteten Knochens. Diese Methode wird vermutlich sehr nützlich sein für quantitative Untersuchungen über den Aktionsmodus anderer Stoffe, welche Knochenresorption und-wachstum beeinflussen, da der Calcitonin-Zusatz es ermöglicht, die Austauschkomponente des aus dem behandelten Knochen freigesetzten Isotopes jederzeit zu messen, ohne daß dabei Gewebe zerstört oder weniger spezifische Inhibitoren des Metabolismus herangezogen werden müssen.
    Notes: Abstract Anin vitro method has been used to investigate the relative effectiveness of calcitonin preparations from different species. It is based on the finding that calcitonin has a marked inhibitory effect on the release of45Ca from prelabelled half-calvariae from 6-day-old mice; this effect is due to the suppression of the endogeneous resorption that is in progress when the bones are explanted, and which continuesin vitro in the absence of calcitonin. Striking differences have been found in the inhibitory effect of calcitonin preparations from either ultimobranchial bodies or from mammalian thyroids. Human calcitonin and porcine standard A calcitonin behave similarly and are about ten times more potent than porcine standard B calcitonin in terms of units based on the rat assay. The calcitonins of ultimobranchial origin are more effective at lower doses for a longer period of time than the thyroid preparations, and are at least ten times more potent than porcine standard A calcitonin or 100 times more potent than porcine standard B. Explants treated with calcitonin release isotope into the medium in a similar manner to that of dead bones, as long as the calcitonin remains effective; for salmon calcitonin there is a twenty-hour period in which the release of isotope from living bones treated with this preparation exchange isotope with the calcium in the medium like frozen-thawed bone. This finding should be very useful in quantitative studies on the mode of action of other compounds that influence bone resorption and accretion, since the addition of calcitonin will enable the exchange component of the isotope released from treated bones, to be measured at any stage without killing the tissue or resorting to less specific inhibitors of metabolism.
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  • 14
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    Calcified tissue international 4 (1969), S. 78-83 
    ISSN: 1432-0827
    Keywords: Bone ; Calcification ; Osteomalacia ; Phosphorus ; Vitamin D
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les effects d'une dose de 1 mg de vitamine D3 (40 000 Unités,) administrée par voie intra-veineuse, ont été étudiés sur l'histologie osseuse et le métabolisme du phosphore chez 19 sujets contrôles dont l'histologie était normale et 28 malades présentant les caractères histologiques de l'ostéomalacie par carence vitaminique D. L'administration de la vitamine D n'a entraîné aucune modification histologique ou biologique significative chez les sujets contrôles. Mais chez les ostéomalaciques, il est apparu en moins de sept jours une augmentation très significative du front de calcification à l'interface tissue-ostéoïde-tissue-calcifié. Cette modification s'accompagnait d'une ascension progressive de la phosphatémie et de la réabsorption tubulaire du phosphore atteignant dans le même délai des valeurs normales.
    Abstract: Zusammenfassung Bei 19 Patienten mit normaler Knochenhistologie und bei 28 Patienten mit histologisch gesicherter Osteomalacie wurde die Wirkung von 1 mg Vitamin D3 (40000 Iv) i.v. auf die Knochenhistologie und den Phosphatmetabolismus untersucht. Bei den Kontrollpatienten konnten keine signifikanten Änderungen nach Vitamin D festgestellt werden, wogegen die Osteomalacie-patienten innerhalb von 7 Tagen eine deutliche Zunahme der Verkalkungszone an der Grenze zwischen Osteoid- und Knochengewebe zeigten. Diese Änderung war von einer fortschreitenden Zunahme des Serum-Phosphates, verbunden mit einer gesteigerten renalen tubulären Rückabsorption des Phosphates begleitet; beide kehrten anschließend gleichzeitig wieder zur Norm zurück.
    Notes: Abstract The effect of a 1 mg dose of intravenous Vitamin D3 (40,000 i.u.) on bone histology and phosphate metabolism was investigated in 19 patients with normal bone histology and 28 patients with histological evidence of osteomalacia. No significant changes occurred in the control patients after Vitamin D but the patients with osteomalacia showed a marked increase, within seven days, in the proportion of osteoid having a calcification front. This was accompanied by a progressive rise in the serum phosphate, which was associated with an increase in the renal tubular reabsorption of phosphate to normal.
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  • 15
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    Calcified tissue international 4 (1969), S. 113-128 
    ISSN: 1432-0827
    Keywords: Bone ; Isotope ; Turnover ; Radiosodium ; Radiocalcium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Après injection intraperitonéale de22Na, la rétention de l'isotope a été déterminée dans l'organisme entier de rasé et dans leur tissu osseux, pendant une période allant jusqu'à 650 jours. Contrairement au45Ca, qui est rapidement concentré dans l'os, puis lentement éliminé, la presque totalité du22Na absorbée par l'os le quitte avec une demie-période de 3–5.5 jours. Cependant, environ 5% de la charge squelettique présente une vitesse de mobilisation lente, avec une demie-période d'environ 700 jours. Etant donné que cette vitesse est comparable à celle de45Ca, il semble que la faible fraction de Na osseux fasse partie de la structure du cristal. Seuls deux des procédés expérimentaux utilisés ont un effet significatif sur la mobilisation du Na. Il s'agit de la consommation prolongée d'un régime pauvre en calcium et d'un changement de l'activité parathyroidienne. Une augmentation du Na alimentaire affecte l'augmentation de la vitesse de mobilisation du sodium dans son composé rapide, alors que le composé lent est peu ou pas affecté. Les calculs effectués, à partir de nos résultats, indiquent que, contrairement au calcium, le squelette ne sert pas de réservoir significatif pour le maintien du milieu liquide extracellulaire.
    Abstract: Zusammenfassung Ratten erhielten intraperitoneal22Na, und die Retention dieses Isotopes wurde während einer Zeitspanne bis zu 650 Tagen im ganzen Körper und in den Knochen bestimmt. Im Gegensatz zu45Ca, welches sehr rasch von den Knochen aufgenommen und dann nur langsam abgegeben wird, verschwindet der größte Teil des vom Knochen aufgenommenen22Na in einer Halbwertzeit von 3–5,5 Tagen. Jedoch zeigen etwa 5% des Knochengerüstes einen sehr langsamen Turnover mit einer Halbwertzeit von ungefähr 700 Tagen. Da dieser Anteil jenem von45Ca vergleichbar ist, kann daraus geschlossen werden, daß diese kleine Fraktion des Na vom Knochen einen integralen Teil der Kristallstruktur ausmacht. Nur zwei der verschiedenen experimentellen Anordnungen, welche ausprobiert wurden, ergaben eine signifikante Wirkung auf den Na-Turnover im Knochen. Diese bestanden einerseits aus einer langzeitigen Verfütterung von Ca-armer Diät, andererseits aus einer Veränderung der Parathyreoidea-Aktivität. Eine Erhöhung der Na in der Nahrung beeinflußte die schnelle Komponente des Na-Turnover im Knochen; sie zeigte aber wenig bis keine Wirkung auf die langsame Komponente. Berechnungen aus unseren Resultaten lassen vermuten, daß — im Gegensatz zum Ca — das Skelet keine signifikante Reservoir-Funktion zur Erhaltung des Na in der extracellulären Flüssigkeit ausübt.
    Notes: Abstract Rats were given22Na intraperitoneally and the retention of the isotope was determined in whole body and in bone for periods up to 650 days. In contrast to45Ca, which is rapidly taken up by bone and then very slowly released, most of the22Na taken up by bone leaves, with a halftime of 3–5.5 days. However, about 5% of the skeletal burden exhibits a very slow turnover, with a half-time of about 700 days. Since this rate is comparable to that of45Ca, it is concluded that this small fraction of bone Na is an integral part of the crystal structure. Only two of the several experimental procedures which were tried produced a significant effect on bone Na turnover. These were prolonged feeding of a low calcium diet and a change in parathyroid activity. An increase in dietary Na affected the fast component of bone Na turnover, but there was little if any effect on the slow component. Calculations from our data suggest that, in contrast to Ca, the skeleton does not serve a significant reservoir function for the support of extracellular fluid Na.
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  • 16
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    Calcified tissue international 3 (1969), S. 107-124 
    ISSN: 1432-0827
    Keywords: Aspidin ; Bone ; Cartilage ; Dentine ; Evolution ; Fossil
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
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  • 17
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    Calcified tissue international 3 (1969), S. 249-260 
    ISSN: 1432-0827
    Keywords: Nucleic acid ; Callus ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Extraction des acides ribonucléiques (RNA) à pH 7,6 et à pH 9,0 en presence du phénol donne 70–75 p. 100 de la teneur en RNA total du tissu osseux du Lapin regénérant après une ostéotomie standardisée, dans l'extrait à pH 7,6 et 10–15 p. 100 dans l'extrait à pH 9,0. 50–70 p. 100 du RNA des diaphyses des os du Lapin qui n'était pas soumis à une ostéotomie sont extraits à pH 7,6 avec une quantité très faible à pH 9,0. Fractionnement des extraits par chromatographie sur 2 p. 100 agarose ou par précipitation avec du NaCl (3M) donne une fraction constituée par du rRNA et characterisée par la composition nucléotidique. Cette fraction correspond à 70 p. 100 du RNA extrait à pH 7,6 et à 65–75 p. 100 du RNA extrait à pH 9,0 de l'os regénérant et à 85 p. 100 du RNA extrait de l'os normal. 10 p. 100 du RNA extrait de l'os regénérant et 5 p. 100 du RNA extrait de l'os normal sont de poids moleculaire plus haut que le rRNA. Les RNA de poids moleculaire plus bas que le rRNA représentent 20 p. 100 du RNA extrait à pH 7,6 et 25–35 p. 100 du RNA extrait à pH 9,0 de l'os regénérant et 10 p. 100 du RNA extrait de l'os normal. Les résultats de centrifugation en gradients de saccharose entre 5 et 20 p. 100 correspondent aux résultats des études de fractionnement.
    Abstract: Zusammenfassung Wird die RNS aus Kaninchenknochengewebe, das sich in der Regenerationsphase nach standardisierter Osteotomie befindet, mit wäßrigen Phenollösungen, extrahiert, so werden bei einem pH-Wert des Extraktes von 7,6 70–75% des totalen RNS-Gehaltes erhalten, gegenüber 10–15% bei einem, pH-Wert von 9,0. Von der normalen Kaninchenradiusdiaphyse ist die Ausbeute an RNS 50–70% bei einer Extraktion im Bereich von pH 7,6 und nur wenige Prozente bei pH 9,0. Eine Fraktionierung der Extrakte mittels Gelchromatographie auf 2% Agarose und durch Behandlung mit 3M Natriumchlorid ergab eine Fraktion, die der rRNS entspricht und durch ihre Nucleotidzusammensetzung charakterisiert ist. Diese Fraktion erreicht bei regenerierenden Knochen 70% der RNS in den bei pH 7,6 gewonnenen Extrakten, 65–75% in jenen bei pH 9,0. während bei normalen Knochen die Ausbeute an RNS 85% bei pH 7,6 betrug. Im Extrakt von pH 7,6 waren beim regenerierenden Knochen 10% und bei normalen Knochen 5% der RNS von höherem Molekulargewicht als rRNS. Kleiner molekular als rRNS waren 20% der RNS in den Extrakten des regenerierenden Knochens bei pH 7,6 und 25–35% bei pH 9,0, während die entsprechenden Extrakte beim normalen Knochen nur 10% dieser kleinmolekularen RNS enthielten. Das Sedimentationsbild mit 5–20% linearen Saccharosegradienten entsprach den Ergebnissen der Fraktionierungsversuche.
    Notes: Abstract Extraction of RNA with aqueous phenolic solutions of pH 7.6 and pH 9.0 yielded 70–75% of the total RNA content of rabbit bone tissue, regenerating after standardized osteotomies, in the pH 7.6 extract and 10–15% in the pH 9.0 extract. From normal rabbit radius diaphysis, 50–70% of the RNA was extracted at pH 7.6 and oly a few per cent at pH 9.0. Fractionation of the extracts by gel chromatography on 2% agarose and by treatment with 3M sodium chloride gave a, fraction corresponding to rRNA and characterized by base composition. This fraction amounted to 70% of the RNA in the pH 7.6 extracts, to 65–75% of the RNA in pH 9.0 extracts from regenerating bone and to 85% of the RNA in pH 7.6 extracts from normal bone. 10% of the RNA in pH 7.6 extracts from regenerating bone and 5% of that in extracts from normal bone were of larger size than rRNA. 20% of the RNA in pH 7.6 extracts and 25–35% in pH 9.0 extracts from regenerating bone and 10% in those from normal bone were of lower size than rRNA. The sedimentation pattern in 5–20% linear sucrose gradients corresponded to the results of the fractionation studies.
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  • 18
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    Calcified tissue international 3 (1969), S. 327-339 
    ISSN: 1432-0827
    Keywords: Bone ; Density ; Analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une technique nouvelle, permettant l'analyse de la densité de faibles quantités de tissus calcifiés pulvérisés, est décrite. Cette technique utilise un analyseur électronique de taille de particules et de volume (»Compteur de Coulter«), pour déterminer les volumes relatifs des fractions pulvérisées, isolées par fractionnement densitométrique, après centrifugation dans des mélanges de solvants organiques. Certains des paramètres, responsables de la distribution densitométrique des poudres d'os, sont étudiés et la reproductibilité du fractionnement et de l'analyse est démontrée. L'application de cette méthode à l'os humain est illustrée par des résultats.
    Abstract: Zusammenfassung Es wird eine neue Technik zur Bestimmung der Dichteverteilung von kleinen Mengen pulverisiertem Knochengewebe beschrieben. Für diese Technik wird ein Apparat zur elektronischen Messung von Partikelgröße und-Volumen (Coulter Counter) verwendet; damit wird das totale relative Volumen der pulverisierten Fraktionen bestimmt, die durch Aufteilung der verschiedenen Dichten mittels Zentrifugieren in Mischungen von organischen Lösungsmitteln isoliert werden. Einige der Parameter, welche die Dichteverteilung von Knochenpulver beeinflussen, wurden untersucht und die Reproduzierbarkeit der Fraktionierung und der Analysen aufgezeigt. Die Anwendung dieser Technik auf Proben von Menschenknochen wird veranschaulicht und die Resultate werden besprochen.
    Notes: Abstract A new technique for the density distribution analysis of small quantities of powdered hard tissues is described. The technique uses an electronic particle size and volume analyser (“Coulter Counter”) to determine the total relative volumes of the powder fractions isolated by centrifugal density fractionation in organic solvent mixtures. Some of the parameters controlling the density distributions of bone powders are examined and the reproducibility of the fractionation and analysis demonstrated. The application of this technique to human bone samples is illustrated and the results discussed.
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  • 19
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    Calcified tissue international 4 (1969), S. 48-59 
    ISSN: 1432-0827
    Keywords: Bone ; Solubility ; Microscopy ; Polarization ; Fluoride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Moyennant und systèmein vitro dont la composition liquide fut variée nous avons pu faire grandir ou dissoudre des cristaux osseux. Ces changements qui se manifestent par des changements de la biréfrigence extrinsique du tissu osseux, ont été suivis à l'aide du microscope polarisant et aussi du microscope électronique. De même l'entrée de45Ca dans les cristaux a été mesurée dans certains cas. Les cristaux osseux sont hétérogènes quant à leur solubilité. Le produit de solubilité du minéral osseux, exprimé par la relationp [Ca]+p[P], est de 6.51±0.07 (σ) mesuré par la microscopie polarisante à l'instant où les changements furent les plus petits. Ce chiffre s'accorde avec les résultats des autres chercheurs qui ont mesuré la solubilité de la poudre osseuse par des autres méthodes. La solubilité des cristaux dans notre système varie inversement avec les concentrations des ions hydroxyliques ou fluors, mais varie directement avec la concentration des ions citriques.
    Abstract: Zusammenfassung Ein Systemin vitro ermöglichte es durch Veränderung der Zusammensetzung der umgebenden Lösung das Wachstum und die Auflösung von Knochenkristallen herbeizuführen. Die hervorgebrachten Veränderungen konnten dank der doppelbrechenden Eigenschaften des Knochengewebes mit dem Polarisationsmikroskop festgestellt werden. Diese Beobachtungen wurden durch Untersuchungen am Elektronenmikroskop und Bestimmungen der45Ca-Aufnahme gestützt. Die Knochenkristalle erwiesen sich als heterogen in bezug auf ihre Löslichkeit. Wenn die hervorgerufene Kristallveränderung im Polarisationsmikroskop minimal war, so entsprach das Gesamtlöslichkeitsprodukt des Knochenminerals, ausgedrückt als p[Ca]+p[P] 6,51±0,07 (S.D.). Diese Resultate bestätigten die Befunde anderer Forscher, welche die Knochenpulverlöslichkeit mittels konventioneller Methoden bestimmten. Die Löslichkeit der Kristalle bei diesem Systemin vitro variierte entgegengesetzt zur Hydroxyl- und Fluoridionenkonzentration, aber im gleichen Sinne wie die Citrationenkonzentration.
    Notes: Abstract Anin vitro system was used to induce growth and dissolution of bone crystals by manipulating the composition of their fluid environment. The induced changes could be detected with the polarizing microscope because of the extrinsic birefringence of the bone tissue. Supporting observations were made with the electron microscope and by determining45Ca uptake. The bone crystals were found to be heterogeneous with regard to their solubility. When induced crystal changes were minimal by polarization microscopy the overall solubility product of the bone mineral expressed asp [Ca]+p[P] was 6.51±0.07 (S.D.). This result corroborated the findings of other investigators who determined bone powder solubility by conventional methods. Solubility of the crystals in thein vitro system varied inversely with hydroxyl ion and fluoride ion concentration, but directly with citrate ion concentration.
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  • 20
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    Calcified tissue international 3 (1969), S. 103-105 
    ISSN: 1432-0827
    Keywords: Mitochondrion ; Calcium ; Excretion ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
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  • 21
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    Calcified tissue international 3 (1969), S. 340-347 
    ISSN: 1432-0827
    Keywords: Bone ; Calcium ; Fluoride ; Ingestion ; compatibility
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des expériences ont été faites sur le rat afin de tester les possiblités d'ingestion perorale simultanée de fluor (F) et de calcium (Ca) en proportions calculées pour traitement de certaines ostéopénies humaines. F sous forme de Na2PO3F et Ca sous forme de gluconate de calcium (CaGluc) n'influençaient pas l'un l'autre quant à l'utilisation par le squelette (fémur). Une viscosité élevée, produite par l'addition d'amidon ou de cellulose carboxyméthylée (CMC) à la solution ou dilution ingérée, augmentait l'utilisation du F même si CaGluc était remplacé par citrate de calcium, qui en soi avait un effet réducteur modéré sur l'utilisation du F. Le glycérophosphate de calcium réduisait fortement l'utilisation du F même en présence de CMC. L'utilisation du F comme NaF était fortement réduite par CaGluc, même en présence de CMC. Les concentrations testées de Na2PO3F, NaF ou CMC n'influençaient pas l'utilisation squelettique de Ca comme CaGluc.
    Abstract: Zusammenfassung Es wurden Rattenexperimente mit markierten Substanzen durchgeführt, um die Auswirkung simultaner peroraler Gaben von Fluor (F) und von Calcium (Ca) zu prüfen, und zwar in einem Verhältnis, das für die Behandlung gewisser menschlicher Osteopenien berechnet wurde. Fluor in Form von Na2PO3F und Ca in Form von Calciumgluconat (CaGluc) interferieren gegenseitig nicht bei der Verwertung durch das Skelet (Femur). Eine hohe Viscosität der eingegebenen Lösung oder der Aufschlämmung, die durch Zusatz von Stärke oder Carboxymethylcellulose (CMC) erzielt wurde, erhöhte die Verwertbarkeit von F sogar wenn CaGluc durch Calciumcitrat ersetzt wurde, welches die F-Verwertung leicht reduzierte. Calcium-glyzerophosphat verminderte die Fluoraufnahme in den Knochen stark, sogar in Anwesenheit von CMC. Die Verwertung von F als NaF war stark herabgesetzt durch CaGluc, selbst beim Vorhandensein von CMC. Die untersuchten Konzentrationen von Na2PO3F, NaF oder CMC hatten keinen Einfluß auf die Calciumaufnahme im Skelet in Form von CaGluc.
    Notes: Abstract Rat experiments with labelled compounds were carried out in order to test the possibilities of simultaneous peroral supply of fluorine (F) and calcium (Ca) in proportions calculated for treatment of certain human osteopenias. F in the form of Na2PO3F and Ca in the form of calcium gluconate (CaGluc) did not interfere with each other's utilisation by the skeleton (femur). A high viscosity produced by adding starch or carboxymethyl cellulose (CMC) to the ingested solution or slurry increased the utilisation of F even when CaGluc was replaced by calcium citrate, which moderately reduced F utilisation. Calcium glycerophosphate strongly reduced F utilisation even in the presence of CMC. The utilisation of F as NaF was strongly reduced by CaGluc, even in the presence of CMC. The tested concentrations of Na2PO3F, NaF or CMC did not influence the skeletal utilisation of Ca as CaGluc.
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  • 22
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    Calcified tissue international 4 (1969), S. 245-256 
    ISSN: 1432-0827
    Keywords: Bone ; Densitometry ; X-ray ; Diet ; Calcium ; Osteoporosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'ingestion quotidienne de calcium of été déterminée en interrogeant 398 individus, âgés de 15 à 90 ans. Le rapport entre l'ingestion de calcium et la minéralisation vertébrale, mesurée par densitométrie radiographique quantitative, est fiable mais cependant significatif. Chez 53 personnes, atteintes d'ostéoporose, comparées à un nombre égal d'individus, d'âges similaires, les valeurs de la minéralisation vertébrale sont 60 pour cent plus faibles que celles du groupe témoin. L'ingestion totale moyenne de calcium est plus faible de 21 per cent chez les ostéoporotiques. Chez les sujets, à ingestion unique de calcium, les patients du groupe témoin ingèrent preque le double de calcium que le groupe des ostéoporotiques. Une diminution moyenne de l'ingestion calcique est notée avec l'âge. Il semble qu'il existe une diminution de l'absorption calcique avec l'âge, l'ostéoporose ou les deux, ainsi qu'un besoin plus grand en calcium chez les sujets âgés pour assurer l'équilibre en calcium. Indépendamment de l'homéostase calcique, un équilibre négatif en calcium augmente la résorption osseuse, et diminue l'ostéogenèse. De nombreux facteurs interviennent dans l'étiologie et la pathogénie de l'ostéoporose: les résultats de cette étude indique que la présence de calcium alimentaire est l'un de ces facteurs.
    Abstract: Zusammenfassung Die tägliche Calciumeinnahme wurde anhand einer Befragung von 398 Personen im Alter von 15–90 Jahren geschätzt. Die Korrelation der Calciumeinnahme und der Mineralisation der Wirbelsäule, wie sie röntgenologisch durch quantitative Messung der Dichte festgestellt wurde, war niedrig, aber durchwegs signifikant. Bei 53 Osteoporose-Patienten, die mit 53 Kontrollpersonen gleichen Alters verglichen wurden, waren die Mineralisationswerte der Wirbelsäule um 60% niedriger als jene der Kontrollgruppe, und die durchschnittlich geschätzte Gesamt-Calciumeinnahme der Osteoporotiker war um 21% tiefer. Von den Exploranden, die Angaben über eine gleichmäßige Calciumaufnahme machten, nahmen die Kontrollpersonen beinahe doppelt so viel Calcium ein als diejenigen mit Osteoporose. Im Durchschnitt wurde eine Verminderung der Calciumeinnahme mit fortschreitendem Alter festgestellt. Es ergibt sich deutlich, daß die Calciumabsorption mit dem Alter, bei Osteoporose oder in der Kombination dieser beiden Faktoren abnimmt, und daß eine größere Calciumeinnahme bei älteren Personen nötig wäre, um eine positive Calciumbilanz aufrechtzuerhalten. Ungeachtet der Komplexität der Calciumhomöostase, kann eine negative Calciumbilanz schließlich dazu führen, daß mehr Knochen resorbiert als gebildet wird. Demzufolge sollte bei erkanntem Bedürfnis eine adäquate Calciumeinnahme gesichert sein. Es ist eine Tatsache, daß viele Faktoren an der Ätiologie und Pathogenese der Osteoporose beteiligt sind; die Resultate dieses Berichtes unterstützen die Wahrscheinlichkeit, daß das Calciumangebot in der Nahrung einer dieser Faktoren ist.
    Notes: Abstract Lifetime daily calcium intake was estimated through interview of 398 individuals from 15 to 90 years of age. The correlation of calcium intake with vertebral mineralization as determined by quantitative radiographic densitometry was low but persistently significant. In 53 persons with osteoporosis matched by age with 53 individuals from the control group, vertebral mineralization values were 60% lower than those of the control group, and the mean estimated total calcium intake in osteoporotics was 21% lower. In those persons reporting a single lifetime calcium intake, the control patients ingested almost twice as much calcium as those with osteoporosis. A mean decrease in calcium intake with advancing years has been shown. Evidence points to a decrease in calcium absorption with age, osteoporosis, or both, as well as a greater need for calcium intake in the elderly to maintain a positive calcium balance. Regardless of the intricacies of calcium homeostasis, a negative calcium balance leads eventually to greater bone resorption than formation, hence the rationality of insuring an adequate calcium intake with recognized nutritional needs. Evidence suggests that many factors are involved in the etiology and pathogenesis of osteoporosis; the data in this report support the likelihood that availability of calcium in the diet is one of them.
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  • 23
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    Calcified tissue international 4 (1969), S. 20-38 
    ISSN: 1432-0827
    Keywords: Calcification ; Epiphyseal Cartilage ; Bone ; Electrolytes ; Organic matrices
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Un procédé de dissection a été mis au point pour permettre l'analyse zonale du cartilage de l'épiphyse des os de la jambe d'un foetus bovin. Des échantillons de tissu complet et lavé venant des différentes zones ont été analysés pour déterminer leur contenu en électrolyte et en constituants organiques, ainsi que pour leur densité, cendres et humidité. Les résultats ont montré que lorsque la quantité de cendres et la densité augmentaient, l'eau contenu dans le tissu diminuait. Les quantités de cendres dans les zones de cartilage en voie de calcification étaient plus grandes qu'il avait été. Quand elles étaient exprimées comme un pourcentage du poids sec, elles étaient les plus importantes dans le cartilage lavé calcifié que dans le autre zones. Au début de la minéralisation du cartilage, la quantité de Na (m moles/l de tissu frais) diminuait tandis que celles du Ca et du P inorganique augmentaient. Les niveaux de Mg augmentaient pendant que la calcification se poursuivait, mais seulement à une faction du taux du Ca et du P. Les rapports Ca/P inorganique étaient les plus grands dans le cartilage au repos (Cartilage non-différentié hyalin), suggérant un lien initiale entre Ca et les chrondromucoprotéines. Cependant, au début de la calcification, pendant la prolifération du cartilage les rapports Ca/P étaient beaucoup plus petits (ca. 1.50) mais augmentaient graduellement avec l'advancement de la minéralisation. Des changements importants survenaient dans la composition de la phase organique, pendant la calcification endochondrale. Comme il a été déterminé par l'analyse de l'hydroxyproline la quantité de collagéne diminuait progressivement pendant la calcification du cartilage, mais augmentait rapidement pendant la formation d'os. Comme il a été déterminé par l'analyse de l'héxosamine et du sulfute les chrondromucoprotéines étaient aux niveaux les plus éléves pendant la prolifération du cartilage et diminuaient constamment au cours de la calcification. Cependant, bien que la calcification était déja très avancée dans le cartilage hypertrophique, de grandes quantites de mucopolysaccharides étaient encore présentes. Les rapports sulfure/hhéxosamine montraient un léger déclin pendant les premiéres étapes de la calcification, mais augmentaient beaucoup pendant le cours de la minéralisation. Les quantités d'acide sialique étaient plus grandes dans le cartilage de l'épiphyse que dans le cartilage au repos ou dans l'os. Les lipides augmentaient rapidement pendant la calcification du cartilage, mais étaient très réduites dans l'os complètement formé. La signification de ces résultats est discutée.
    Abstract: Zusammenfassung Eine Seziermethode, die eine Schichten-Analyse der Beinepiphysenplatte von Rinderfeten erlaubt, wurde entwickelt. Proben vor und nach Waschen des Gewebes der verschiedenen Schichten werden untersucht in bezug auf Elektrolyte und organische Bestandteile, als auch in bezug auf Dichte, Aschengehalt und Feuchtigkeit. Die Resultate zeigten eine Zunahme des Aschengehaltes und der Dichte, während der Wassergehalt abnahm. Unerwartet hoch waren die Aschenwerte im in Verkalkung begriffenen Knorpel. Ausgedrückt in Prozent Trockengewicht, ergab gewaschener, verkalkter Knorpel den höchsten Wert aller Zonen. In den Frühstadien der Knorpelmineralisation nahm der Natriumgehalt (m Mol/l Frischgewebe) ab, während Ca und anorganischer P zunahmen. Mit fortschreitender Verkalkung erhöhte sich auch der Magnesium-Spiegel, allerdings nur zu einem Bruchteil des Ausmaßes, in welchem Ca und P zunahmen. Die höchsten Ca/P anorg. Verhältnisse wurden im Ruheknorpel (undifferenzierter hyaliner Knorpel) gefunden, was auf eine initiale Bindung von Ca durch Chondromucoproteine hinweist. Die Ca/P-Verhältnisse proliferierenden Knorpels waren jedoch bei Verkalkungsbeginn viel tiefer (ca. 1.50). Diese nahmen allerdings mit fortschreitender Mineralisierung stetig zu. In der endochondralen Verkalkungsphase fanden markante Veränderungen in der Zusammensetzung des organischen Anteils statt. Basierend auf der Hydroxyprolinanalyse nahm der Collagengehalt in der knorpeligen Verkalkungsperiode fortschreitend ab, während er jedoch bei der Knochenbildung rasch zunahm. Die an Hand von Hexosamin- und Schwefelanalysen bestimmten Chondromucoproteingehalte ergaben Höchstwerte im proliferierenden Knorpel und fielen stetig ab mit zunehmender Verkalkung. Trotz der im hypertrophischen Knorpel schon weit fortgeschrittenen Verkalkung waren immer noch große Mengen an Mucopolysacchariden vorhanden. Die Schwefel/Hexosamin-Verhältnisse zeigten eine minimale Abnahme in den frühen Verkalkungsphasen, nahmen jedoch markant zu bei fortschreitender Mineralisation. Der Sialinsäurespiegel war im Epiphysenknorpel, verglichen mit demjenigen des Ruheknorpels oder Knochens, erhöht. In der knorpeligen Verkalkungsphase nahmen die Lipide rasch zu, während jedoch die Werte des vollständig ausgebildeten Knochens stark vermindert waren. Die Bedeutung dieser Ergebnisse wird besprochen.
    Notes: Abstract A dissection procedure has been devised to permit zonal analysis of the epiphyseal plate of fetal calf leg bones. Samples of whole and washed tissue from the various zones were analyzed for their content of electrolyte and organic constituents, as well as for density, ash and moisture. Results showed that as ash content and density increased, water content decreased. Ash levels in calcifying cartilage zones were unexpectedly high. When expressed as a percentage of dry weight, washed calcified cartilage had the highest content of any zone. In the early stages of the mineralization of cartilage, Na content (mmoles/l of fresh tissue) decreased as Ca and inorganic P increased. Magnesium levels increased as calcification proceeded, but only at a fraction of the rate of Ca and P. Ratios of Ca/inorganic P were highest in resting cartilage (non-differentiated hyaline cartilage), suggesting an initial binding of Ca to chondromucoproteins. However, at the onset of calcification in proliferating cartilage, Ca/P ratios were much lower (ca. 1.50), but gradually increased with advancing mineralization. Marked changes occurred in the composition of the organic phase during endochondral calcification. As determined by hydroxyproline analysis, collagen content progressively decreased during cartilaginous calcification, but increased rapidly during bone formation. As determined by hexosamine and sulfur analysis, chondromucoproteins were at highest levels in proliferating cartilage and decreased steadily as calcification increased. However, although calcification was already well advanced in hypertrophic cartilage, large amounts of mucopolysaccharide still were present. Sulfur/hexosamine ratios showed a slight decline during the early stages of calcification, but increased markedly with further mineralization. Sialic acid levels were elevated in epiphyseal cartilage over those in resting cartilage or bone. Lipids increased rapidly during cartilaginous calcification, but were greatly reduced in fully-formed bone. The significance of these findings is discussed.
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  • 24
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Magnetic non-equivalence of methylenic protons in A—CH2—CH3 groups were studied for several types of compounds. Results are compared with respect (1) to the nature of heteroatom A:A = O and A = S and (2) to the structure of the local dissymmetry element: asymmetric carbon, ketal group and allenic system. Influence of substitution is discussed in relation to conformational problems. Furthermore a variation of the methylene geminal coupling constant with substituents of carbon α to OEt is observed.
    Notes: La non-équivalence magnétique des protons méthyléniques de groupements A—CH2—CH3 est étudiée dans plusieurs séries de composés. Les effets sont comparés d'une part dans les séries A = O et A = S, d'autre part dans les composés présentant un carbone asymétrique, un carbone de type cétal ou une dissymétrie allénique. L'influence de la substitution sur le carbone en α de AEt est discutée en relation avec les conformations. Une variation de la constante de couplage entre les protons méthyléniques géminés en function de la nature des substituants lointains est mise en évidence.
    Additional Material: 6 Tab.
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  • 25
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Activation energies Eα and free enthalpies of activation ΔG
    Notes: Mittels der Temperaturabhängigkeit der Protonenresonanzsignale wurden für 1.3-Dioxane, 1.3-Oxathiane und 1.3-Dithiane mit ein und zwei Paaren geminaler Methylsubstituenten Geschwindigkeitskonstante k, freie Aktivierungsenthalpie ΔG
    Additional Material: 2 Ill.
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  • 26
    ISSN: 0030-4921
    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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    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 1 (1969), S. 88-89 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 28
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 29
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    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 1 (1969), S. 90-92 
    ISSN: 0030-4921
    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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    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 1 (1969) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 31
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    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 1 (1969), S. 93-99 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The theory for deceptive simplicity in the NMR spectra of oriented molecules is discussed in terms of degeneracy of subspectra. The conditions for the degeneracy of AB, AB2 and AA′BB′ spectra leading to deceptive simplicity in the spectra of the type ABX, AB2X, AA′BB′X and AA′XX′ are reported.It is shown that the conditions for deceptive simplicity are easily fulfilled for ABX, AA′BB′X and AA′XX′ cases. It is further demonstrated that deceptive simplicity is not so common in AB2X spectra.The proton spectra of partially oriented 2,4,5-trichloronitrobenzene (AB) and 2,6-dibromo-pyridine (AB2) are use to illustrate degeneracy and those of p-chloro- and p-bromo-fluorobenzenes are reported to demonstrate deceptive simplicity.
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  • 32
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    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 1 (1969), S. 101-108 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An NMR study of some bridged bicyclo and tricyclo compounds yielded unusual spectra with respect to solvent effects and virtual coupling. As is the general case for most large polycyclic systems a complete analysis of the spectrum is not possible and the structural details derived from NMR are based on a partial analysis of the spectrum. If the accessible resonances correspond to protons adjacent to methylene groups, the resonance patterns and the chemical shifts may be strongly dependent upon solvent. For 6-endo-hydroxy, bicyclo[2.2.1]heptane-2,endo-carboxylic acid lactone (1), 6-endo-hydroxy, 2-exo-methyl-bicyclo[2.2.2]octane-2-endo-carboxylic acid lactone (2), and exo-3,4,exo-8,9-diepoxy, endo-tricyclo[5,2,1,02,6]decane (3), resonances for each fall in this class and the change induced by solvent are attributed to virtual coupling as well as a change in the overall splitting pattern.
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  • 33
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    Organic Magnetic Resonance 1 (1969), S. 109-123 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The barriers to rotation about the C—N bond in eighteen substituted N,N-dimethylbenzamides have been determined by complete line shape analysis of the NMR spectra of the N,N-dimethyl protons. The barriers have been correlated with the substituent constants σ and σ+. It has been shown that polar solvents increase the barrier in N,N-dimethylbenzamide.Acid catalysis of rotation about the amide C—N bond in N-(p-N,N-dimethylcarboxamidobenzyl)-pyridinium bromide has been investigated. 18O exchange studies show that catalysis is due to N-protonation rather than the formation of a tetrahedral intermediate. The rate of rotation is a function of the Hammett acidity function, H0, and the water activity, and it is shown that proton exchange between the N- and O-protonated species involves the intermediacy of a water molecule.The differences in chemical shifts for the non-equivalent N, N-dimethyl groups of the benzamides are also a function of the substituents. Possible explanations of this phenomenon are discussed.
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  • 34
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A variable temperature, proton magnetic resonance study has been made of complexes of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, and 2,6-dimethylpyridine with borane and boron trifluoride. By lowering the temperature and slowing ligand exchange, separate resonance signals can be observed for bulk and complexed molecules of the base. A direct comparison of the complexing abilities of these ligands was made by studying them in pairs with borane or boron trifluoride. The complexing abilities, as estimated from the NMR data, decreased in the order: 4-MePy 〉 3-MePy 〉 Py 〉 2-MePy 〉 2,6-MePy. This trend was interpreted in terms of steric effects and the basic strengths of these molecules towards boron trifluoride.
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  • 35
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    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 1 (1969) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 36
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The ring inversion of cyclohexane derivatives with one, two and three pairs of geminal methyl and alkoxyl groups has been studied by investigations of the temperature dependence of the NMR signals.The rate of the inversion depends on the number and the relative positions of the ligand pairs as well as on their size. A single pair of geminal ligands has only a very slight effect on the inversion rate. Two ligand pairs hinder the inversion when they are in the 1 and 4 positions relative to one another, but facilitate it when they are in the 1 and 3 positions. In both cases the effects are smaller with methoxyl groups than with methyl groups.Three ligand pairs significantly increase the inversion rate when they are in the 1, 3 and 5 positions, but reduce it when they are in the 1, 2 and 4 positions.The effect of 1,3 substituents is attributed to an increase in the energy of the ground state of the molecules whereas the effect of 1,4 arranged substituents is attributed to an increase in the energy of the transition state of the chair inversion.
    Notes: Mittels der Temperaturabhängigkeit der Protonenresonanzsignale wurde die sesselinversion von Cyclohexanderivaten mit ein, zwei und drei Paaren geminaler Methyl- und Alkoxylgruppen untersucht.Die Geschwindigkeit der Sesselinversion hängt von der Zahl und der relativen Stellung der Ligandenpaare sowie von der Größe der Liganden ab.Ein Paar geminaler Liganden verändert die Inversionsgeschwindigkeit nur unwesentlich.Zwei Liganden-Paare erschweren die Inversion, wenn sie in 1- und 4-Position zueinander stehen, erleichtern sie jedoch, wenn die in 1- und 3-Position zueinander angeordnet sind. Beide Effekte sind bei Methoxylgruppen kleiner als bei Methylgruppen.Drei Liganden-Paare erhöhen die Umklapphäufigkeit besonders stark, wenn sie in 1-, 3- und 5- Position zueinander stehen, vermindern sie hingegen, wenn sie in 1-, 2- und 4-Position angeordnet sind.Der Effekt 1,3-ständiger Substituenten wird auf Erhöhung des Energieinhaltes des Grundzustandes der Molekeln, der Effekt 1,4-ständiger Substituenten auf Erhöhung des Energieinhaltes des Übergangszustandes der Sesselinversion zuriückgeführt.
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  • 37
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    Organic Magnetic Resonance 1 (1969), S. 189-189 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 38
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: For the interpretation of experimental data on the activation energy and free activation enthalpy for the inversion of cyclohexane and its di-, tetra- and hexa-methyl derivatives, model calculations were made to determine the ‘relative’ energies of the ground, intermediate and transition states of the molecules. For this purpose Hendrickson's model was extended so that with internal molecular variables (bond lengths, valence and torsional angles) the topography and the ‘relative’ energy of every possible unsymmetrical conformation could be included.To obtain optimal agreement between the calculated values and the experimental results a total of 17 different combinations of potential functions for deformation of valence angles, torsional angles and H—H interactions were used. By application of the extended calculating procedure it was found that for cyclohexane the half-chair conformation is not, as until now assumed, the only transition conformation in chair inversion, but that there are numerous other unsymmetrical transition conformations with similar energies.The calculations for methyl cyclohexanes showed that for molecules with synaxial arrangement of methyl groups the relative energy of the chair form is considerably increased. The chair form is however still the most stable, even in the case of 1,1,3,3,5,5-hexamethylcyclohexane. The most favourable twist conformations are about 2.6 to 6.5 kcal/mole energy richer.Calculation of activation energies showed that, with synaxial arrangement of two or more methyl groups, the relative energy of the transition conformation is less markedly increased than is that of the ground state, with the result that the activation energy is reduced in comparison with that for cyclohexane.
    Notes: Zur Interpretation der experimentell bestimmten Werte der Aktivierungsenergie bzw. der freien Aktivierungsenthalpie der Ringinversion wurden für Cyclohexan, 1,1-Dimethyl-, 1,1,3,3- und 1,1,4,4-Tetramethyl- sowie 1,1,3,5,5-Hexamethylcyclohexan Modellberechnungen des ‘relativen’ Energieinhalts von Grund-, Zwischen- und Übergangskonformationen durchgeführt. Dazu wurde das Hendrickson'sche Rechenmodell so erweitert, daß mit molekülinternen Variablen (Bindungsabständen, Valenz- und Torsionswinkeln) die Topographie und der ‘relative Energieinhalt’ jeder beliebigen unsymmetrischen Konformation berechnet warden können.Zur optimalen Anpassung der berechneten Daten an die experimentellen Ergebnisse wurden insgesamt 17 verschiedene Kombinationen von Potentialfunktionen für Deformation von Valenzund Torsionswinkeln und H—H-Wechselwirkung verwendet.Bei Anwendung des erweiteren Rechenverfahrens auf die Cyclohexanmolekel ergab sich, daß die halbsesselähnliche Konformation nicht, wie bisher angenommen, einzige Übergangskonformation der Sesselinversion ist, vielmehr gibt es außerdem unendlich viele unsymmetrische Übergangskon-formationen gleichen Energieinhalts. Die Rechnungen ergaben für die Methylcyclohexane, daß bei Molekülen mit synaxialer Anordnung von Methylgruppen der relative Energieinhalt des Sessels zwar stark angehoben ist, der Sessel ist jedoch in allen Fällen selbst bei den Molekeln des 1,1,3,3,5,5-Hexamethylcyclohexans die stabilste Konformation. Die günstigsten Twistkonformationen sind um 2,6 bis 6,5 kcal/mol energiereicher. Bei der Berechnung der Aktivierungsenergie wurde gefunden, daß bei synaxialer Stellung von mindestens zwei Methylgruppen der relative Energieinhalt der Übergangskonformation weniger stark angehoben ist als derjenige der Sesselform, wodurch die Aktivierungsenergie im Vergleich zum Cyclohexan erniedrigt wird; bei 1,4-Stellung der Substituenten wird dagegen der relative Energieinhalt der Übergangskonformation stärker angehoben als der des Grundzustandes, die Aktivierungsenergie wird erhöht.
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  • 39
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    Organic Magnetic Resonance 1 (1969), S. 209-212 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The two stereochemically distinct two-bond carbon-13- hydrogen coupling constants J(13C—CH), for α-chlorostyrene-α-13C have been shown to be of similar magnitude but opposite sign (-6.3 and +5.6 Hz). A simple additivity relationship which adequately reproduces all the reported J(13C—CH) values for chloroethylenes has been found.
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  • 40
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    Organic Magnetic Resonance 1 (1969), S. 213-227 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proton NMR spectra of 1-substituted 2,4-dimethylbenzenes (2), 1-substituted 2,6-dimethylbenzenes (3) and 1-substituted 2,4,6-trimethylbenzenes (4) were determined and the SCS values compared with those of monosubstituted benzenes (1). SCS of 1 are assumed to be primarily due to the effects of π-electron charge density, substituent electric field and substituent diamagnetic anisotropy, and the van der Waals interaction: thus \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm SCS = SCS}_{\pi {\rm}} + {\rm SCS}_{\rm E} + {\rm SCS}_{\rm A} + {\rm SCS}_{\rm V} $$\end{document} When, however, the substituent is sterically hindered, then: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm SCS}^{\rm '} {\rm = SCS}_{{\rm \pi}^{\rm '}} {\rm + SCS}_{{\rm E}^{\rm '}} {\rm + SCS}_{{\rm A}^{\rm '}} {\rm + SCS}_{\rm V} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ = {\rm c}_{\rm \pi} {\rm SCS}_{\rm \pi} {\rm + c}_{\rm E} {\rm SCS}_{\rm E} {\rm + c}_{\rm A} {\rm SCS}_{\rm A} {\rm + c}_{\rm V} {\rm SCS}_{\rm V} $$\end{document} where cπ∼V may be constants predictable from the theories associated with each component. By estimating SCSπ∼V or cπ∼V, a quantitative separation of SCS into their components was attempted. It is shown, however, that the data available, as well as the nature of this approach, cannot necessarily be sufficient for this purpose.Various effects which might also contribute to the proton NMR chemical shifts of sterically hindered molecules are also discussed.
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  • 41
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    Organic Magnetic Resonance 1 (1969), S. 229-237 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The proton and 13C—H satellite spectra of five diethyl haloacetals have been analyzed and their spectral parameters obtained. The parameters for the ethoxy methylene protons indicate the extent of their magnetic nonequivalence. It has been found that these parameters are dependent on the degree of halogen substitution in the group Z, which is bonded to the central carbon atom, and correlate well with the corresponding group electronegativity values, a′ z, proposed by Huheey. The parallel behavior of the methylenic J(C—H) and chemical shifts indicates that a primarily through-bond mechanism is responsible for propagation of both the electronic and symmetry effects observed. Transmission factors calculated from the spectral data agree with independent estimates reasonably well, thus supporting the conclusions reached here.
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  • 42
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The non-equivalence of ethyl, benzyl and isopropyl groups fixed on nitrogen atoms in 2-and 3-pyrazolines, pyrazolidines and pyrazolidones depends on the assymetry existing in the molecule. The asymmetric centres are either a ring carbon atom, a quaternary nitrogen atom (protonation, quaternarization) or a tertiary nitrogen atom (slow nitrogen inversion). The nitrogen inversion process was observed only in the case of pyrazolidines (possibility of inversion at the two adjacent nitrogens) and of pyrazolidones (inversion of the ‘non-amidic’ nitrogen). The inversion is temperature-dependent and is affected by substituents.
    Notes: La non-équivalence de groupements éthyle, benzyle et isopropyle fixés sur les azotes de pyrazolines-2 et 3, de pyrazolidines et de pyrazolidones est fonction de l'asymétrie existant dans la molécule. Celle-ci peut provenir soit d'un carbone du cycle, soit de l'un des azotes rendu asymétrique par protonation, quaternarisation ou simplement par ralentissement de son inversion, Ce dernier phénomène n'a été observé que dans le cas des pyrazolidines (possibilité d'inversion de deux azotes adjacents) et des pyrazolidones (inversion de l'azote non amidique): il est fonction des substitutions et des variations de température.
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  • 43
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    Organic Magnetic Resonance 1 (1969), S. 278-278 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 44
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    Organic Magnetic Resonance 1 (1969), S. 279-280 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 45
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    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 1 (1969) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 46
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    Organic Magnetic Resonance 1 (1969), S. 281-293 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have examined the 19F NMR spectra of a number of oxygen-containing fluorocarbon products and obtained a comprehensive set of 19F chemical shift values, which enabled us to determine the influence of an oxygen atom bonded to a fluorocarbon group on the 19F chemical shift. The influence of neighbouring fluorocarbon groups, either directly connected or separated by an oxygen atom, was also considered.Our results may be summarized as follows. An oxygen atom bonded by a single bond (ether type bond) to a fluorine substituted carbon atom decreases the 19F chemical shift, as does the introduction of a further fluorine atom. Considering two adjacent fluorocarbon groups, a variation of x ppm in the 19F chemical shift of one of the two groups gives a variation of 0·12 x ppm in the opposite sense on the 19F chemical shift of the other group. If the two groups are connected by an ether oxygen atom, the effect is only about 0·06 x ppm.
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  • 47
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    Organic Magnetic Resonance 1 (1969), S. 295-303 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-precision line measurements and tickling were shown to yield information, often not accessible, on the assignment and signs of spin coupling constants. For pentafluorothiophenol-d, this information was obtained for the three meta-JFF's. Relative to C6F5SH, the 19F resonances in C6F5SD experienced an upfield ‘isotope’ shift.
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  • 48
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The two C-4 protons of reduced nicotinamide adenine dinucleotide (NADH) produce an AB NMR spectrum at 100 MHz as well as at 220 MHz. This observation allows an upper limit of 50 sec-1 to be placed on the mean rate of interconversion of the two folded forms of NADH invoked to account for the magnetic non-equivalence of the C-4 protons. The interpretation of non-equivalence of the C-4 protons in terms of the various equilibria among folded and unfolded forms of NADH and its possible significance in the mechanism of action of dehydrogenase enzymes is discussed. It is suggested that one folded form of NADH is strongly favored thermodynamically over the other and that the resulting magnetic non-equivalence of the C-4 protons is of doubtful significance in explaining the stereospecificity of dehydrogenase enzymes toward the nicotinamide ring.
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  • 49
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: NMR spectral parameters are reported for benzofurazan, 1,2,3- and 2,1,3-benzothiadiazole, and 1-methyl- and 2-methyl-benzotriazole. The coupling constants are discussed in connection with the aromaticity of these compounds and the occurrence of partial bond fixation.
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  • 50
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    Organic Magnetic Resonance 1 (1969), S. 319-327 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The NMR spectra of fifteen para-substituted acetanilides, XC6H4·NH·CO·CH3 (X = NH·CO·Me; NH2; CO·OEt; COOH; Cl; OEt; F; H; OMe; CH3; NO2; C6H5; —N=N—C6H5; Me3Si), have been recorded. δCH3 and δNH are linearly related to Hammett's σp constant. The coupling J (o-H—H) between aromatic protons is mainly dependent on σR0. J(13C—H), in methyl group is approximatively constant in the series.
    Notes: Les spectres de RMN de quinze acétanilides para-substitués XC6H4·NH·CO·CH3 (X = NH·CO·ME; NH2; CO·OEt; COOH; Cl; OEt; F; H; OMe; CH3; NO2; C6H5;—N=N—C6H5; Me3Si) ont été étudiés. Il y a une relation linéaire entre δCH3 et δNH et les constantes σP de Hammett. Le couplage J(o-H—H) entre les protons aromatiques est relié plutôt à σR0. La constante J (13C—H) dans le groupe CH3, est indépendante de X.
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  • 51
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    Organic Magnetic Resonance 1 (1969), S. 329-335 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proton magnetic resonance spectra of methylene dichloride solutions containing N-methyl morpholine and sulphur dioxide have been studied as a function of temperature. Complex formation reduces the rate of interchange of magnetic sites via inversion at nitrogen but increases the rate of ring inversion. The conformational preference of the complex is discussed. It is suggested that interaction with SO2 may be a useful general method of studying nitrogen inversion.
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  • 52
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    Organic Magnetic Resonance 1 (1969), S. 341-342 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 53
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    Organic Magnetic Resonance 1 (1969), S. 337-340 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The meso or threo configuration of diastereoisomeric molecules is elucidated on the basis of respective NMR spectra of either isomers. The symmetry relationship (according to Raban and Mislow) between protons or groups are not identical in each isomer, and the consequent differences in chemical shifts and spin-coupling constants permit assignment of configurations.
    Notes: La configuration meso ou thréo de molécules diastéréoisomères est déterminée à partir des spectres RMN respectifs xde chaque isomère. Les relations de symétrie (Raban et Mislow), qui existent entre protons ou groupes de ces molécules sont différentes par chaque diastéréoisomère d'un couple donné et ces différences se traduisent dans les déplacements chimiques et constantes de couplage mis en jeu. Des attributions de configuration sont ainsi rendues possibles.
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  • 54
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    Organic Magnetic Resonance 1 (1969), S. 343-344 
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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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  • 55
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    Organic Magnetic Resonance 1 (1969), S. 344-344 
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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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  • 56
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    Organic Magnetic Resonance 1 (1969), S. 344-344 
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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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  • 57
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    Organic Magnetic Resonance 1 (1969) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 58
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    Organic Magnetic Resonance 1 (1969), S. 467-470 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The NMR spectrum of phenylacetylene has been studied in the nematic phase of a mixture of 50% 4-methoxy benzylidene 4-amino-α-methyl cinnamic acid-n-propyl ester and 50% anisole-p-azophenyl-n-capronate at 30°C. Ratios of interproton distances have been derived.
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  • 59
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The substituent effect on proton resonances and vicinal H, H-coupling constants in benzene derivatives is studied using linear regression analysis. The change in shielding observed on substitution, relative to the proton resonance in benzene, Δσ, can be expressed as \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta\sigma = - 1.04 \times 10^{- 12} {\rm E}_{\rm Z} - 1.08 \times 10^{- 18} {\rm E}^{\rm 2} + 9.17\Delta \rho + 0.18. $$\end{document}. This equation enables calculations of substituent effects on the basis of the dipolar and quadratic field effect (Ez, E2) and the π-charge density changes on the neighbouring C-atom (Δρ).The vicinal coupling constants show no correlation with the HMO-π-bond order. A linear regression using the well known dependence of the coupling constant on substituent electronegativity yields \documentclass{article}\pagestyle{empty}\begin{document}$$ ^3 {\rm J = 7}{\rm .63 + 0}{\rm .508}\Delta \alpha - 0.096\Delta \beta $$\end{document} where ΔEα and ΔEβ are the changes in electronegativity caused by substitution in α- or β-position, respectively, to the HCCH-fragment considered.
    Notes: Der Einfluß von Substituenten auf die Protonenresonanzen und die vicinalen H, H-Kopplungskonstanten in Benzolderivaten wird mit Hilfe linearer Ausgleichsrechnungen untersucht. Für die relativ zur Protonenresonanz des Benzols auftretende Abschirmungsänderung Δσ bei der Substitution wird die Beziehung \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta\sigma = - 1.04 \times 10^{- 12} {\rm E}_{\rm Z} - 1,08 \times 10^{- 18} {\rm E}^{\rm 2} + 9,17\Delta \rho + 0,18. $$\end{document} angegeben, die eine Berechnung der Substituenten-Effektes mit Hilfe des dipolaren und quadratischen Feldeffektes (Ez, E2) und der π-Ladungsdichte-Änderung am benachbarten C-Atom (Δρ) erlaubt.Die vicinalen Kopplungskonstanten lassen sich mit der HMO-π-Bindungsordnung nicht korrelieren. Eine Ausgleichsrechnung unter Benutzung der bekannten Abhängigkeit der Kopplung von der Substituenten-Elektronegativität liefert \documentclass{article}\pagestyle{empty}\begin{document}$$ ^3 {\rm J = 7}{\rm .63 + 0}{\rm .508}\Delta \alpha - 0.096\Delta \beta $$\end{document} wobei ΔEα und ΔEβ die durch Substitution bedingte Änderung der Elektronegativität in α- bzw. β-Stellung zum betrachteten HCCH-Fragment bedeuten.
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  • 60
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The confromations of the unsaturated seven membered ring in 4,4,6,6-tetradeuterium-1,2-benzocycloheptene-(1) (1) and five benzocycloheptene derivatives were determined by NMR spectroscopy. For all investigated compounds at -80°C only one conformer was present in detectable quantity. By analysis of the NMR data - molecular symmetry, coupling constants and chemical shift - it can be shown that the conformation is always the chair form. The free conformational enthalpy of both the other conformations with boat or twist form of the ring is for all six compounds more than 1.8 kcal/mole.The experimental results agree with those from model calculations: thus for benzocycloheptene, the 5,5-dimethyl derivative (2) and the 4,4,6,6-tetramethyl derivative (4) the lowest energy was found for the chair conformation; the second most stable conformations were found to be the boat for 1 and 4, and the twist form for 2.
    Notes: Für 4.4.6.6-Tetradeuterium-1.2-benzocyclohepten-(1) (1) und fünf Benzocyclo-heptenderivate wurde PR-specktroskopisch die Konformation des ungesättigten Siebenringes bestimmt. Bei allen untersuchten Verbindungen liegt bei -80° nur ein Konformeres in nachweisbarer Menge vor. Durch Auswertung PR-spektroskopisch bestimmter Daten - Molekel-Symmetrie, Kopplungskonstanten, chemische Verschiebungen - kann gezeigt werden, daß dieses Konformere Sesselform hat. Die freie Konformationsenthalpie der beiden anderen Konformeren mit Wannen- bzw. Twist-Form des Siebenringes beträgt bei allen sechs Verbindungen mehr als 1,8 kcal/Mol.Mit den experimentellen Ergebnissen stimmen diejenigen von Modellrechnungen überein: Für die Molekeln des Benzocycloheptens sowie des 5.5-Dimethylderivates (2) und der 4.4.6.6-Tetramethylverbindung (4) wurde für die Sesselkonformation der niedrigste Energieinhalt berechnet; als zweitstabilste Konformation wurde bei 1 und 4 die Wanne, bei 2 hingegen die Twist-Form ermittelt.
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  • 61
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Various complexes of boron trifluoride and typical organo-phosphours compounds have been investigated using proton and fluorine resonance (at variable temperature) and boron and phosphorus resonance. In BF3, boron resonance is insensitive to the complex strength, but fluorine resonance suggests the possibility of various types of complexes on the phosphorus group or, additionally on the heteroatoms (e.g. oxygen, nitrogen) of the molecule. These complexes are probably σ type. Proton chemical shifts in the organo-phosphorus compounds follow the same trends as in similar complexes of amines, esters etc.; these perturbations may be mainly due to magnetic anisotropy effects; proton-phosphorus couplings conversely follow changes in phosphorus electronegativity.
    Notes: On a étudié, en résonance du proton et du fluor (à température variable) ainsi qu'en résonance du bore et du phosphore, un certain nombre de complexes entre BF3 et des composés organo-phosphorés typiques. En ce qui concerne BF3, la résonance de bore reste insensible à la force du complexe; par contre, la résonance du fluor suggéère l'existence de plusieurs types de complexes, soit sur le groupe phosphoré, soit sur les hétéroatomes (par example N, O) de la molécule. Ces complexes sont vraisemblablement de type σ pur. Le déplacement chimique des protons dans la molécule organo-phosphorée subit sensiblement les mêmes perturbations que dans les autres molécules complexables (amines, esters, etc.); ces perturbations peuvent provenir avant tout d'effets d'anisotropie magnétiques; par contre, les couplages proton-phophore suivent la modification de l'électronégativité de ce dernier.
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  • 62
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    Organic Magnetic Resonance 1 (1969), S. 491-491 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 63
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    Organic Magnetic Resonance 1 (1969), S. 481-489 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of line width and chemical shift vs. temperature for amide and hydroxyl proton magnetic resonance signals from: barbituric acid, dialuric acid, parabanic acid, alloxan and alloxan monohydrate dissolved in anhydrous dimethyl sulfoxide-d6 are reported. The behavior of the amide signals shows that, between 20 and 65°C, none of the compounds listed exhibits lactim-lactam tautomerism. The amide proton resonance in uracil has also been investigated. The signal is a closely spaced, equal intensity, doublet due to the non-equivalence of H(1) and H(3). Again, no evidence of tautomerism is observed. Activation energies for the hydroxyl resonances in dialuric acid and alloxan monohydrate indicate hydrogen bonding between solute and solvent. The results of simple LCAO-MO calculations are in accord with the experimental conclusions concerning tautomeric equilibria.
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  • 64
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    Biological Mass Spectrometry 2 (1969) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 65
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A system is described in which computer techniques are used to carry out major steps in the procedure for interpretation of high-resolution mass spectral data. These steps include identification and evaluation of the molecular ion, neutral fragments lost from the molecular ion, and characteristic ion series, followed by elucidation of specific structural details using a sub-routine for the particular compound class selected. The technique shows promise of not only increasing the interpreter's efficiency, but of providing more specific and detailed structural information from the spectral data.
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  • 66
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    Biological Mass Spectrometry 2 (1969), S. 17-31 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of twenty-six commercially available medicinal phenothiazines have been determined at high resolution. In each compound, the side chain attached to the 10-position of the phenothiazine ring contains nitrogen and fission of the C—C bond α to this nitrogen gives in most cases the base peak. Some of the compounds are also substituted at the 2-position and this substituent generally remains intact, though some substituents such as acetyl, propionyl, methoxyl and methylthio can undergo fragmentation. Fragmentations fall into three groups; those which give ions representing a part of the side chain; those which give ions representing the intact phenothiazine ring with part of the side chain attached; those which give ions representing a partially fragmented ring system.
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  • 67
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    Biological Mass Spectrometry 2 (1969), S. 33-36 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Under electron-impact, N-alkyl trifluoracetamides exhibit peaks due to [CF3]+ and [M — CF3]+. Ions corresponding to [COCF3]+ are absent. The base peak in many straight chain derivatives occurs at m/e 126 due to alkyl radical loss from the molecular ion; the mass of this ion rising to m/e 140 in the α-substituted N-sec-butyltrifluoracetamide and to m/e 154 in the tert-butyl derivative. High resolution measurements on a number of peaks indicate that they originate by loss of HF from other fragment ions.
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  • 68
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    Biological Mass Spectrometry 2 (1969), S. 37-47 
    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 3-indazolone (I), 1-acetyl-3-acetoxyindazol (II), 1,2-diacetyl-3-indazolone (III), 1-methyl-3-indazolone (IV), 2-methyl-3-indazolone (V), 2-methyl-3-indazolone-N-d-1 (VI), 3-methoxy-indazole (VII), 1-ethyl-3-indazolone (VIII), 1-carbethoxy-3-indazolone (IX), 1-carbethoxy-2-methyl-3-indazolone (X), 2′-carboxyethyl-3-indazolone (XI), 1-oxo-2,3-dihydropyrazolo-(1,2-α)-3-indazolone (XII) and 1-ethyl-3-indazolone-N-d-2 (XIII) are reported. The loss of an ·N2R radical from the parent radical ion in indazolone and the alkyl indazolones occurs more readily than the loss of a formyl radical, and no loss of HCN is observed from the parent radical ion. Mass spectral data can be used to distinguish between N-methyl and O-methyl derivatives of 3-indazolone.
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  • 69
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    Biological Mass Spectrometry 2 (1969), S. 81-103 
    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 exo-2-norbornyl chloride, 1- and 2-methyl exo-2-norbornyl, exo-camphenilyl, apoisobornyl, bornyl and isobornyl chloride, and camphene hydrochloride, α- and β-fenchyl chloride and fenchene hydrochloride, and exo-isofenchyl chloride and 2,5,5-trimethyl exo-2-norbornylchloride, and camphene and α-fenchene have been examined at 12 to 16 and 80° eV and at 30 to 49 and 80°, or higher temperatures. Wagner-Meerwein rearrangements occur very readily in the ion source and compounds related by these rearrangements give very similar fragmentation patterns. Thermal decompositions are important with the tertiary chlorides especially at higher source temperatures. The rates of methanolysis of some of these chlorides were measured.
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  • 70
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    Biological Mass Spectrometry 2 (1969), S. 63-79 
    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 several fluoroalkyl, fluoroalkenyl and fluoroacyl complexes of manganese, rhenium, iron and ruthenium carbonyls are described. After loss of carbonyl groups, fluoroalkyl compounds eliminate an olefin, with formation of metal halide species. A trifluorovinyl complex shows a novel elimination of a carbon atom to give an ion postulated to be a difluorocarbene-metal fluoride; the occurrence of difluorocarbene-metal ions in the spectra of some related complexes is also discussed. The spectra of the acyl complexes show little evidence of elimination of the acyl carbonyl group; the major process is fission of the CO—Rf bond with loss of a fluoroalkyl radical and formation of the cationic metal carbonyl, e.g. π-C5H5M(CO)3+ (M = Fe or Ru). The relevance of thermal or photochemical model reactions to processes occurring in the mass spectrometer is discussed.
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  • 71
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    Biological Mass Spectrometry 2 (1969), S. 49-61 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Changes in the mass spectra with inlet temperature were used in this work to demonstrate the dependence of keto-enol tautomerism of acetylacetone, 3-methyl acetylacetone and 3-allyl acetylacetone on temperature.The largest dependence of temperature were shown by the ion [M — 42]+. arising from a McLafferty type rearrangement and by the ion [M — Me]+ resulting from simple α-cleavage. The ion [M — 42]+. peak increases with the temperature of the inlet system while the ion [M — Me]+ peak decreases. By assuming that the ion [M — 42]+. represents the keto form and that the ion [M — Me]+ represents the cis-enol form (stabilized by the hydrogen bond) one sees that the direction of the intensity variation of these peaks with temperature is in accord with the expected change of keto-enol tautomerism with temperature. A quantitative correlation on the basis of the above assumptions is also approached.Recording of the mass spectra of these three β-diketones at different energies of the incident electrons enables us to estimate whether or not the particular ions present in the mass spectra result from energetically favourable processes.The variation of the intensities of the peaks with the temperature of the inlet at different electron energies is also discussed.
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  • 72
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    Biological Mass Spectrometry 2 (1969), S. 105-119 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: α-Trifluoracetamino carbon ions are important fragments in the mass spectra of N-Trifluoracetyl α-amino acids and their derivatives. They fragment by eliminating neutral molecules. This breakdown is mainly influenced by the structure of their substituents. Several of these ions show some remarkable skeletal rearrangements.
    Notes: α-Trifluoracetaminocarbonium-Ionen treten als charakteristische Bruchstücke in den massenspektren von N-Trifluoracetyl-α-aminosäuren und deren Derivaten auf. Sie zerfallen unter Eliminierung stabiler Neutralmolekeln, wobei in erster LInie die Struktur ihres Substituenten entscheidenden Einfluß ausübt. Im Zuge dieser Fragmentierungen kommt es bei einer Reihe von Ionen zu bemerkenswerten Strukturumlagerungen.
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  • 73
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    Biological Mass Spectrometry 2 (1969), S. 135-135 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 74
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    Biological Mass Spectrometry 2 (1969), S. 136-136 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 75
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    Biological Mass Spectrometry 2 (1969), S. 121-134 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: As a result of high resolution mass measurements, calculation of metastable ions, and investigation of specifically deuterated compounds the fragmentation is discussed of some α-substituted N-methyl benzylamides containing different N-acyl groups. α-Cleavage leads to the formation of N-methyl α-acylamino carbon ions which show skeletal rearrangement. The intensity of the rearranged ions depends on the structure of the N-acyl group. Migration of the α-methyl group is observed in the mass spectra of N-acetyl and N-p-Cl-benzoyl N-methyl-α-phenylethylamide.
    Notes: Der massenspektrometrische Zerfall einiger α-substituierter N-Methylbenzylamide mit verschiedenen N-Acylgruppen wird anhand der Ergebnisse aus hochauflösender Massenbestimmung, Berechnung der metastabilen Ionen Untersuchung spezifisch deuterierter Verbindungen diskutitert. Dabei wird die Strukturumlagerung der durch α-Spaltung entstandenen N-Methyl-α-acylaminocarboniu-Ionen nachgewiesen. Sie ist von der Art der N-Acylgruppe abhängig. In den Massenspektren von N-Acetyl-bzw. N-p-Cl-Benzoyl-methyl-α-phenyläthylamid wird die Wanderung der α-Methylgruppen beobachtet.
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  • 76
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    Biological Mass Spectrometry 2 (1969) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 77
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    Biological Mass Spectrometry 2 (1969), S. 137-156 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 78
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    Biological Mass Spectrometry 2 (1969), S. 175-194 
    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 dehydration and solvolysis products obtained from β-amyrin and glycyrrhetic acid were studied. With the exception of those resulting from ‘backbone’ rearrangement, they exhibited conventional fragmentation due to the ring C chromophore, like the parent alcohols. Only those products with a contracted ring A suffered loss of an isopropyl radical. In the latter type, special fragmentation features were exhibited by the isopropylcyclopentene and by the isopropylidene products. These differences enabled the assignment of probable structures for two unknown derivatives.
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  • 79
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The C8H9+-ion, formed from the molecular ions of 2-phenyl-1-bromoethane, 1-phenyl-1-bromoethane and of 1-phenyl-1-nitroethane by loss of the bromine atom and of the nitro group, splits off a molecule of acetylene after an almost complete randomization of hydrogens, as proved by deuteration. An eight-membered ring structure for the C8H9+-ion is proposed to explain these results.By loss of the nitro group from the molecular ions of 1-phenyl-1-nitropropane and of 1-phenyl-2-nitropropane the well-known phenylated cyclopropane ion3 (C9H11)+ is generated. Mass spectra of analogues, specifically deuterated in the side-chain, show that in this ion a randomization of hydrogen atoms in the cyclopropane ring as well as a hydride transfer from the cyclopropane ring to the phenyl cation occur.
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  • 80
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    Biological Mass Spectrometry 2 (1969), S. 209-212 
    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 deuterated species shows that both the isomeric ions [CH2=SH]+ and [CH3—S]+ are formed in the ratio 2:1 from CH3SH; the ions [CH3CH=SH]+ and [CH3CH2S]+ in the ratio 0·8:1 from CH3CH2SH; and [CH2=OH]+ and [CH3—O]+ in the ratio 6·7:1 from methanol.The heats of formation of [CH3S]+ and [C2H5S]+ are of the order of 222 and 203 Kcal.mole-1 respectively. The isomeric ions cannot be distinguished on thermodynamic grounds.
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  • 81
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    Biological Mass Spectrometry 2 (1969), S. 195-207 
    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 several compounds obtained during the process of Stork's isoxazole synthesis9 as well as the related isoxazoles have been investigated. The fragmentations of simple alkyl isoxazoles are nicely formulated via azirine intermediates. A striking difference between the spectra of isoxazoles and those of methylfurans as to the relative abundance of [M  -  l] peaks is noteworthy. The very low abundance of these peaks in the former reflects the unique character of isoxazole nucleus due to the preferential cleavage of N—O linkage rather than a benzylic C—H bond rupture. If an alkyl substituent is present at 4-position in 3,5-dimethylisoxazoles, strong peaks at m/e 110, 68 and 43 are common in their spectra. The analyses of metastable transitions and high resolution measurements have demonstrated that the formation of these ions can be interpreted by a mechanism involving the cleavage of N—O linkage.
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  • 82
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    Biological Mass Spectrometry 2 (1969), S. 213-221 
    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 series of aliphatic polynitro compounds are reported and discussed. The fragmentation patterns of aliphatic nitro and polynitro compounds are similar in that no appreciable molecular ion current is observed; however, there are several other features in the fragmentation of aliphatic polynitro compounds which differ from that of nitroalkane spectra. Both series of compounds studied-C(NO2)x(CH3)4-x, where x = 4 to 0 and C2(NO2)x(CH3)6-x, where x = 6,4,2-show a decrease in the number and intensity of alkylions with an increase in the NO+ and NO2+ ion current as x increases. The main ions resulting from the more nitrated compounds are [NO]+, [NO2]+, [CO2]+. and [CH3CO]+, whose noncharged counterparts are the principal species produced in the detonation of these compounds. This similarity of the products of the two processes suggests the use of mass spectroscopy for the investigation of the initial explosive processes. The principal fragmentation pathways of the polynitroalkanes have been elucidated by exact mass measurements and the observation of metastable ion transitions.
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    Biological Mass Spectrometry 2 (1969), S. 223-239 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 2,6-di-unsaturated carbonyl compounds, two successive, site-specific hydrogen transfers are necessary to account for the loss of carbon atoms 1, 2, 3 and 4, together with one hydrogen from C-8. The deuterated methyl geranate required for this study was readily converted to pseudo-ionone, in which a similar fission was shown to occur. Previous predictions about the β-ionone mass spectrum2 have been shown to be substantially correct, and its similarity to the mass spectra of benzylidence acetones is pointed out.
    Additional Material: 8 Ill.
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  • 84
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    Biological Mass Spectrometry 2 (1969), S. 241-248 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mass-spectral and n.m.r. analysis of thiophenes labeled by exchange with deuteriosulfuric acid establishes that exchange at the 2 and 5 positions is essentially complete before any deuterium is incorporated at positions 3 and 4. Thus, such exchange is a satisfactory procedure for position-specific labeling. Mass spectra of the labeled thiophenes show that about 60% of the [CHS]+ ion yield is derived from molecular ions that have not undergone prior rearrangement. The remaining 40% arises by a path or paths in which the four hydrogen atoms lose position identity. Other decomposition paths contributing to the mass spectrum are characterized by more nearly complete scrambling of hydrogens.
    Additional Material: 5 Tab.
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  • 85
    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 2-substituted 8-hydroxyquinolines and related compounds are reported. Fragmentation pathways based upon interpretation of spectra and metastable transitions for 8-quinolinol; 2-methyl-8-quinolinol; 4-methyl-8quinolinol; 2-hydroxymethyl-8-quinolinol; 2-aminomethyl-8-quinolinol; 8-quinolinol-2-carboxaldehyde; 8-quinolinol-2-carb-oxaldehyde oxime; and 8-quinolinol-2-carboxaldehyde tert-butylimine are discussed, as are dissociations in the related compounds 2-hydroxymethyl quinoline and quinoline-2-carboxaldehyde oxime. It is suggested that the molecular ions of 2-substituted-8-quinolinols undergo rearrangement to a substituted azatropylium ion prior to dissociation. An ion of m/e 89 has been observed in these spectra and is considered to be characteristic of the quinoline nucleus bearing an X-substituent in any position, where X = OR, SR, NH2 etc. (R = H, CH3, etc).
    Additional Material: 7 Ill.
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  • 86
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    Biological Mass Spectrometry 2 (1969), S. 283-298 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: When a fragmentation takes place in mass spectrometry, the positive charge remains on the fragement with the lowest ionization potential. This criterion, which has been indicated previously for the alkane series is shown to be generally true.
    Notes: Lors d'une rupture en spectrométrie de masse, la charge positive demeure préférentiellement sur le fragment de potentiel d'ionisation le plus bas. Ce critère, qui fut mis en évidence sur les alcanes, a été généralisé à divers types de fragmentations.
    Additional Material: 21 Ill.
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  • 87
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    Biological Mass Spectrometry 2 (1969), S. 299-308 
    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 ionization and fragmentation of six C6H10 structural isomers have been studied in order to determine the effect of isomerism upon their mass spectrometric behavior. The 70 eV mass spectra, metastable transitions and appearance potentials of the principal ions are reported. Significant differences between the mass spectra of the six isomers were observed; however, metastable transition and appearance potential data indicate that the fragmentation path-ways are the same for all the C6H10 molecules. Experimentally determined ionization potentials for the structural isomers are presented and compared to ionization potentials calculated by the bond orbital method. Utilizing fragmentation pathways deduced from general features in the mass spectra and from observed metastable transitions, we calculated heats of formation (ΔHf) for the observed principal ions and compared these values to ΔHf values for isomeric ions from other molecules.
    Additional Material: 2 Ill.
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  • 88
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    Biological Mass Spectrometry 2 (1969), S. 309-315 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of the non-benzenoid aromatic heterocycles 2H- and 2-methyl-2H-cyclopenta[d]pyridazine and several deuterated analogs have been analyzed. The majority of the nitrogen lost from these heterocycles occurs as HCN OR H2CN. The deuterium labeling suggests a rearrangement of the molecular ion prior to fragmentation.
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  • 89
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    Biological Mass Spectrometry 2 (1969), S. 325-330 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of the styryl ion \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm PhCH = }\mathop {\rm C}\limits^{\rm + } {\rm H} $\end{document} in the mass spectra of some cinnamic compounds is shown to occur via the intermediate formation of the cinnamoyl ion \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Ph} - {\rm CH} = {\rm CH} - {\rm C} \equiv \mathop {\rm O}\limits^{\rm + } $\end{document} rather than by direct cleavage of the bond α to the double bond.
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  • 90
    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 allphatic ketones are drastically altered following substitution of a trifluoromethyl entity adjacent to the carbonyl group (II and III) or attachment to the γ-carbon atom (V). Loss of the trifluoromethyl group by α-cleavage far exceeds the alternative elimination of an alkyl radical. Virtually complete repression of the McLafferty rearrangement process (I → a) occurs when a CF3 group is attached to the γ-carbon atom. A fluorine atom is not transferred in lieu of hydrogen in the McLafferty rearrangement as demonstrated by the mass spectrum of 1,1,1,7,7,7-hexafluoroheptan-4-one (IV). Rationalization for these results are presented as is a description of the syntheses of several hitherto unknown fluorinated ketones.
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  • 91
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    Biological Mass Spectrometry 2 (1969), S. 331-333 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a series of straight chain aliphatic ketones which has been studied, it has been shown that the structural requirement for loss of water from the molecular ions produced by electron-impact is an alkyl group of seven or more carbon atoms attached to the carbonyl function.
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  • 92
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    Biological Mass Spectrometry 2 (1969), S. 425-426 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 93
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    Biological Mass Spectrometry 2 (1969), S. 427-429 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that FI mass spectra can serve to elucidate some structural features and determine the molecular weights of mono- and oligosaccharides.
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  • 94
    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 thioglycollic acids and esters are reported and discussed. The spectra of compounds of the type X·CH(Y)·S·CH2·COOR(X 〉 Y) contain skeletal rearrangement fragments with the composition R·Y·C2H3SO+. Ions produced by simple cleavage processes may be usefully correlated with structure.
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  • 95
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    Biological Mass Spectrometry 2 (1969) 
    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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  • 96
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structure elucidation of organic compounds is only one of the applications of mass spectrometry to chemistry. Important subjects are also mass spectrometric quantitative analysis of mixtures of inorganic and of organic compounds, determination of isotopes and related problems. In ‘Massenspektrometrie’, edited by H. Kienitz, all these applications are discussed together with an excellent introduction to the function of mass spectrometers and the techniques of measurement. This book contains a lot of information and stimulation for mass spectroscopists and chemists, and is especially recomended for use in analytical laboratories.
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  • 97
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    Biological Mass Spectrometry 2 (1969), S. 433-445 
    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 tetrazole, all isomers of monomethyl- and dimethyltetrazole, several trifluoromethyl substituted tetrazoles, as well as deuterated analogs, were recorded. Loss of N2 was the important fragmentation of the molecular ions of tetrazole and 2-methyl substituted tetrazoles; however, HN2 loss was more important for 1-methyl substituted tetrazoles. The 1-methyl-tetrazoles showed molecular ion peaks while the 2-methyltetrazoles exhibited an unprecedented [M + 1] peak with no molecular ion.
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  • 98
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    Biological Mass Spectrometry 2 (1969), S. 481-519 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 99
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    Biological Mass Spectrometry 2 (1969), S. 447-466 
    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 25 triphenylmethyl (trityl) substituted compounds have been recorded. The trityl cation m/e 243 appears as a peak of major intensity for all classes of compounds examined; these contained trityl-carbon, trityl-nitrogen, trityl-oxygen or trityl-sulfur bonds. Fragmentation of the non-trityl portion of the molecules produced simple ions whose origin was predictable or of low intensity. A mechanism for the decay of the trityl cation is presented which is based upon retention of the α-carbon. Supporting evidence was afforded by mass spectral analysis of (C6H5)313CH in which all fragments from the trityl cation appear to retain nearly all of the 13C.
    Additional Material: 6 Ill.
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  • 100
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    Biological Mass Spectrometry 2 (1969), S. 467-479 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanisms for the major fragmentations obtained with selected substituted uracils are discussed. Interpretation of data was facilitated by use of metastable peaks, high-resolution data, and low-voltage spectra.The major fragmentation obtained with N-alkyl substituted uracils, when the alkyl group contains 2 or more carbons, is due to cleavage of the alkyl substituent. This cleavage is accompanied by a rearrangement of 1 or 2 hydrogens from the alkyl group to the uracil ring. Possible mechanisms for the rearrangements are discussed. It was found that the molecular ion of 1- and 3-alkyl substituted uracils (where the alkyl group has 2 or more carbons) does not undergo the expected ‘retro Diels-Alder Reaction’. Instead, the odd-electron ion formed by loss of the alkyl substituent with a single hydrogen rearrangement undergoes this reaction (loses HNCO). Since it is formed as a secondary reaction product, the relative abundance of the ‘retro Diels-Alder’ fragment is low compared to what is obtained in the spectra of the simple uracils.The ‘retro Diels-Alder Reaction’ can be used to differentiate between 2- and 4-thiouracils, and between 1- and 3-methyl and phenyl substituted uracils. It was found that 1- and 3-alkyl substituted uracils (alkyl group of 2 or more carbons) can be differentiated by the mass of the M-alkyl fragment since the 3-substituted compounds give predominantly a double hydrogen rearrangement and the 1-substituted compound gives mainly a single hydrogen rearrangement. In addition the intensity of the molecular ion, relative to the M-alkyl ion, is considerably stronger in the 1-substituted uracils.
    Additional Material: 12 Ill.
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