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  • 1975-1979
  • 1970-1974  (6,015)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 10 (1972), S. 82-90 
    ISSN: 1432-0827
    Keywords: Calcium ; Phosphate ; Precipitation ; Kinetics ; Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé La cinétique de la formation et de la transformation des précipités de phosphate de calcium, obtenus en mélangeant de volumes égaux de solutions à 6×10−3 M de calcium total et/ou phosphate total est étudiée à 25°C. Les solutions de phosphate sont préajustées à un pH de 7.4. Les changements de pH et de turbidité des solutions sont suivis simultanément en fonction du temps. Les précipités sont isolés à des intervalles de temps variables et caractérisés par diverses méthodes physico-chimiques. Initialement un précipité avec un rapport molaire Ca/P de 1.5, amorphe aux rayons X et en diffraction électronique, est formé. Le spectre IR indique la présence de PO 4 3− et de HPO 4 2− . Après une période métastable, on observe la précipitation d'un matériel cristallin dans ou sur la phase amorphe. Vingt quatre heures après préparation de l'échantillon les précipités présentent surtout les caractères du phosphate octocalcique.
    Abstract: Zusammenfassung Die Kinetik der Bildung und Transformation von Calciumphosphat-Niederschlägen wurde bei 25°C untersucht. Es wurden dazu gleiche Volumen von Lösungen gemischt, bei einer Konzentration von 6×10−3M totales Calcium und/oder totales Phosphat. Die Phosphatlösungen wurden zuerst auf pH 7,4 eingestellt. Veränderungen des pH und Trübung der Lösungen wurden gleichzeitig als eine Funktion der Zeit aufgezeichnet. Niederschläge wurden in verschiedenen Zeitintervallen isoliert und mit verschiedenen physiko-chemischen Methoden charakterisiert. Am Anfang wurde ein Niederschlag mit einem molaren Ca/P-Verhältnis von 1,5, im Röntgenbild und in der Elektronendiffraktion amorph, gebildet. Infrarotspektren deuteten die Anwesenheit von PO 4 3− - und HPO 4 2− -Ionen an. Nach einer metastabilen Periode erfolgte ein Niederschlag aus kristallinem Material innerhalb oder auf der amorphen Substanz. 24 Std nach der Herstellung der Proben zeigten die Niederschläge in der Hauptsache die Charakteristiken von Octocalciumphosphat.
    Notes: Abstract The kinetics of the formation and transformation of calcium phosphate precipitates obtained by mixing equal volumes of solutions, 6×10−3 M in total calcium and/or total phosphate was investigated at 25°. The phosphate solutions were preadjusted to pH 7.4. Changes of the pH and turbidity of the solutions were followed simultaneously as a function of time. Precipitates were isolated at various time intervals and characterized by different physicochemical methods. Initially a precipitate with a molar Ca/P ratio of 1.5, amorphous to X-ray and electron diffraction was formed. IR spectra indicated the presence of PO 4 3− and HPO 4 2− ions. After a period of metastability, precipitation of a crystalline material within or upon the amorphous matter occurred. Twenty four hours after sample preparation the precipitates showed mainly the characteristics of octacalcium phosphate.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Research in experimental medicine 158 (1972), S. 75-84 
    ISSN: 1433-8580
    Keywords: Renal Potassium Excretion ; Insulin ; Glucose ; Osmotic Diureses ; Kalium (renale Ausscheidung) ; Insulin ; Glucose ; Osmotische Diurese
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Mannit in hypertonischer Lösung ruft bekanntlich eine osmotische Diurese mit erhöhter Natrium- und Kaliumausscheidung hervor. Hypertonische Glucoseinfusionen (Blutzuckerwerte 280–380 mg%) dagegen führen bei nieren- und stoffwechselgesunden Probanden trotz Entwicklung einer osmotischen Diurese zu einer verminderten Kaliumausscheidung bei nur gering gesteigerter Natriurese. Zusätzlich verabfolgtes Insulin verstärkt den kaliumretinierenden Effekt in Abhängigkeit von seiner Dosierung. Die Ergebnisse lassen eine direkte Insulinwirkung auf die renale Kaliumausscheidung annehmen. Unter den genannten Versuchsbedingungen wird ein Quotient für U/PKalium 〈 1 und gleichzeitig eine verminderte Natriumausscheidung bestimmt. Bei Patienten mit stärker eingeschränktem Glomerulumfiltrat (chronische Pyelonephritis) wird die bereits bestehende endogene osmotische Diurese durch intravenöse Glucosezufuhr (Blutzucker um 400 mg%) verstärkt und führt zu erheblicher Kalium- und Natriummehrausscheidung bei signifikant sinkenden Plasmaspiegeln dieser Elektrolyte.
    Notes: Summary In contrast to the increased excretion of sodium and potassium in mannitol-diuresis in healthy men, hypertonic glucose-infusion (bloodsugar 280 to 380 mg%) causes in spite of osmotic diuresis a decrease of potassium excretion and only a small loss of sodium. Insulin applied in addition raises this effect according to its dosage. It is suggested, that insulin modifies renal potassium excretion either by increasing reabsorption and/or decreasing secretion. Under these conditions the ratio U/Ppotassium was found 〈 1. In patients with markedly reduced glomerular filtration rate by chronic pyelonephritis endogenous osmotic diuresis is enhanced by glucose-infusion (bloodsugar 400 mg%). Now an increasing excretion both of potassium and sodium was found, while plasma levels of these ions decreased significantly.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 8 (1972), S. 260-266 
    ISSN: 1432-0428
    Keywords: Insulin ; radioimmunoassay ; total IRI in insulin-treated diabetics ; acid ethanol extraction of insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé On décrit une méthode de routine pour le dosage de l'IRI (insuline immunoréactive) totale chez les diabétiques traités par l'insuline. La méthode comprend une extraction à l'acide-éthanol, très simple, pendant laquelle l'IRI liée aux anticorps est dissociée et séparée ainsi que l'IRI »libre« des protéines sériques, anticorps compris. La récupération de l'IRI par cette méthode est aux environs de 80%. Après la séparation, l'IRI totale isolée est mesurée par un dosage immunologique qui se sert de l'éthanol afin de séparer l'I125-insuline libre de celle liée aux anticorps. Chez 169 malades diabétiques traités par l'insuline à des doses allant de 6 à 120 unités par jour, l'IRI totale sérique à jeun était de 6 à 4374 μU/ml, avec une moyenne de 392 μU/ml. Pendant le traitement par l'insuline le taux de l'IRI totale est passé des niveaux normaux, enregistrés pendant les deux premiers mois, à des niveaux plus éleévs qui se stabilisent 5 mois environ apres le début du traitement. L'augmentation de l'IRI coïncide avec la formation d'anticorps. Les malades insulino-résistants présentent des valeurs très hautes d'IRI.
    Abstract: Zusammenfassung Für die Bestimmung des Gesamt-IRI (immunoreaktiven Insulins) bei Diabetikern, die mit Insulin behandelt wurden, wird eine Routinemethode beschrieben. Die Methode schließt eine einfache SäureÄthanol-Extraktion ein, wobei das antikörpergebundene IRI dissoziiert und zusammen mit dem „freien“ IRI von den Serumproteinen, einschließlich den Antikörpern, getrennt wird. Bei diesem Verfahren werden etwa 80% des IRI wiedergefunden. Nach der Trennung wird das isolierte Gesamt-IRI immunologisch gemessen. Für die Trennung des freien von dem an Antikörper gebundenen125I-Insulin wird Äthanol verwendet. Bei 169 Diabetikern, die mit 6 bis 120 E Insulin/Tag behandelt wurden, lag das Nuchternserum-Gesamt-IRI zwischen 6 und 4374 μE/ml (Mittelwert 392 μE/ml). Im Laufe der Insulinbehandlung stieg das Gesamt-IRI von Normalwerten, die während der ersten 2 Monate registriert wurden, auf ein höheres Niveau an, das sich nach etwa 5 Monaten Behandlungsdauer stabilisierte. Der Anstieg des IRI erfolgte gleichzeitig mit der Bildung von Antikörpern. Bei insulinresistenten Patienten ergaben sich sehr hohe IRI-Konzentrationen.
    Notes: Summary A routine method is described for the determination of total IRI (imraunoreactive insulin) in insulintreated diabetics. The method involves an easy acid ethanol extraction, whereby antibody-bound IRI is dissociated and separated, together with the “free” IRI from the serum proteins and the antibodies. The recovery of IRI in this procedure is about 80%. After the separation, the isolated total IRI is measured in an immunoassay, using ethanol for the separation of free and antibody bound125I-insulin. In 169 diabetic patients treated with insulin in doses of from 6 to 120 units/day, the fasting serum total IRI was between 6 and 4374 μU/ml, with a mean of 392 μU/ml. During treatment with insulin, the level of total IRI increased from normal values, registered during the first two months, to a higher level which became stable after about 5 months of treatment. The increase in IRI occurred simultaneously with the formation of antibodies. Insulin-resistant patients showed very high IRI levels.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 10 (1972), S. 171-197 
    ISSN: 1432-0827
    Keywords: Amorphous ; Crystalline ; Calcium phosphate ; Chemistry ; Composition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des échantillons non lavés de phosphate de calcium amorphe (ACP) contiennent une fraction labile, non remplaçable, riche en phosphate acide avec un rapport Ca/P faible: cette fraction est perdue de façon irréversible au cours du lavage. De l'ACP frais, précipité entre pH 6.6–10.6, varie dans un rapport molaire Ca/P de 1.18 à 1.50 et dans un rapport HPO 4 2− /P total de 33.0% à 10.1%. A pH 7.40, de l'ACP frais a un rapport molaire Ca/P de 1.36±0.02 et contient 22.8 (±2.2)% HPO 4 2− . Les résultats obtenus avec du précipité non lavé ne peuvent s'expliquer par du Ca2+ emprisonné et de l'HPO 4 2− ou du Na+, Cl− et CO 3 2− exogènes. Les phosphates de calcium amorphes constituent une classe de sels ayant des caractères chimiques variables et des propriétés physiques identiques, comparables au verre. Le CaHPO4·xH2O non cristallin peut être un ACP, surtout au cours des phases précoces de formation. A des pH physiologiques, l'ACP se transforme en petits cristaux applatis contenant de fortes quantités de phosphate acide facilement remplaçable. Le fait de laver la couche de surface produit un changement chimique dans les nouveaux cristaux: des cristaux non lavés donnent des diagrammes de diffraction d'apatite peu cristallins, ainsi que des spectres infra-rouges peu nets, intermédiaires entre des apatites et du phosphate octocalcique. Des explications structurales sont proposées et les compositions minérales amorphe/cristalline de l'os et du cartilage sont recalculées.
    Abstract: Zusammenfassung Ungewaschene Proben von amorphem Calciumphosphat (ACP) enthalten eine unersetzliche labile Fraktion, welche reich an saurem Phosphat ist und ein niederes Ca/P-Verhältnis hat und welche während des Waschprozesses unwiderruflich verloren geht. Natives ACP, welches im pH-Bereich 6,6–10,6 ausgefällt wurde, variierte im molaren Ca/P-Verhältnis zwischen 1,18 und 1,50 und in HPO 4 2− /totales P zwischen 33,0 und 10,1%. Bei pH 7,40 hatte natives ACP ein molares Ca/P-Verhältnis von 1,36±0,02 und enthielt 22,8 (±2,2)% HPO 4 2− . Die Werte beim ungewaschenen Niederschlag rühren weder von aus dem Überstand aufgenommenem Ca2+ und HPO2−, noch von außen kommendem Na+, Cl− und CO 3 2− her. Die amorphen Calciumphosphate werden als eine Klasse von Salzen erkannt, welche veränderliche chemische, aber identische glasartige physicochemische Eigenschaften haben. Nicht kristallines CaHPO4·xH2O kann auch ein ACP sein, besonders in den frühen Bildungsstadien. Bei physiologischem pH verwandelt sich ACP in kleine plattenförmige Kristalle, welche große Mengen von leicht ersetzbarem saurem Phosphat enthalten. Das Waschen dieser Oberflächenschicht erzeugte chemische Veränderungen in den resultierenden Kristallen; ungewaschene Kristalle zeigten ein Diffraktionsmuster, das nur schwach demjenigen des kristallinen Aspatites glich, aber ein schlecht aufgelöstes Infrarotspektrum, welches zwischen Apatit und Octocalciumphosphat war. Es werden strukturelle Erklärungen für alle diese Phenomena diskutiert, und revidierte amorph/kristalline Mineralzusammensetzungen von Knochen und Knorpel wurden neu berechnet.
    Notes: Abstract Unwashed samples of amorphous calcium phosphate (ACP) contain an irreplaceable labile fraction, rich in acid phosphate and low in Ca/P ratio, which is irreversibly lost during the washing process. Native ACP precipitated in the pH range 6.6–10.6 varied in Ca/P molar ratio from 1.18 to 1.50 and in HPO 4 2− /total P from 33.0% to 10.1%. At pH 7.40, native ACP had a Ca/P molar ratio of 1.36±0.02 and contained 22.8 (±2.2)% HPO 4 2− . Unwashed precipitate data could not be attributed to either trapped supernatant Ca2+ and HPO 4 2− or extraneous Na+, Cl−, and CO 3 2− . The amorphous calcium phosphates are recognized as a class of salts having variable chemical but identical glass-like, physicochemical properties. Non-crystalline CaHPO4·xH2O may also be an ACP, especially during early formative stages. At physiological pH, ACP transforms to small platy crystals containing large amounts of readily-replaceable acid phosphate. Washing this surface layer produced chemical alterations in the resultant crystals; unwashed crystals had poorly-crystalline apatitic diffraction patterns but exhibited poorly-resolved infrared spectra intermediate between apatite and octacalcium phosphate. Structural explanations for all these phenomena are discussed, and revised bone and cartilage amorphous/crystalline mineral compositions have been re-calculated.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 26 (1972), S. 62-72 
    ISSN: 1432-2072
    Keywords: Delta-9-Tetrahydrocannabinol ; Marihuana ; Timing ; Audition ; Monkeys ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In two experiments, macaques were trained to respond differentially to either the duration of a visual stimulus or to the frequency of an auditory clicker. In the duration discrimination experiment, delta-9-tetrahydrocannabinol (delta-9-THC) was administered acutely in doses from 1 to 16 mg/kg, producing dose-related decrements in accuracy of the discrimination performance, and a reduction in the rate at which the animals initiated discrimination trials. In both the duration and auditory discrimination experiments, chronic daily administrations of 2 to 16 mg/kg of delta-9-THC produced an initial decrement in accuracy and rate of trial initiation. Both measures showed some development of tolerance, tending to return to baseline levels, however, the time course of tolerance was different for the measures, with the rate of trial initiation recovering more quickly than accuracy. No differences in response to the drug were attributable to the different modalities used in these two experiments.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 27 (1972), S. 163-169 
    ISSN: 1432-2072
    Keywords: Marihuana (Cannabis) ; (−)δ 9-trans-Tetrahydrocannabinol (δ 9-THC) ; Psychopharmacology ; Operant Behavior ; Schedule of Reinforcement
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Four rats were trained to barpress for water reinforcement under a variable interval 60 sec schedule. Nine acute administrations of (−)δ 9-trans-tetrahydrocannabinol, in amounts ranging from 0.25 to 16.0 mg/kg, produced dose-related effects on responding; overall response rate increased at lower doses, while higher doses produced ataxia and a complete suppression of responding. Increased response rates reflected changes both in response spacing and in the lengths of post-reinforcement pauses. It was concluded that marihuana has a biphasic effect on variable interval water-reinforced behavior in rats.
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  • 7
    ISSN: 1432-2072
    Keywords: Marihuana (Cannabis) ; (−)δ 9-trans-tetrahydrocannabinol (δ 9-THC) ; Psychopharmacology ; Operant Behavior ; Schedule of Reinforcement
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Eight chimpanzees emitted panel push responses under a procedure in which three operant schedules of positive reinforcement, each associated with a different stimulus, were presented successively. The fixed ratio (FR) schedule required the emission of 40 responses for reinforcement. Reinforcement under the differential reinforcement of low rate (DRL) schedule was delivered only for a response that followed the immediately preceding response by 10 or more sec. No responses were reinforced under the extinction or time out from reinforcement (TO) schedule. The behavioral effects produced by a marihuana extract distillate containing a known amount of (−)δ 9-trans-tetrahydrocannabinol (δ 9-THC) were compared with those produced by a totally synthesized δ 9-THC. On four separate drug days each chimpanzee was orally administered one of the two compounds 2.5 h prior to experimentation in amounts yielding 1.0 mg/kg δ 9-THC. Only the DRL schedule performance was significantly affected by either drug compound. Both the marihuana extract and the synthetic δ 9-THC produced a statistically significant decrease in the percentage of correct DRL responses. However, no statistically significant differences between the drug effects produced by the two δ 9-THC dose forms were obtained.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Pflügers Archiv 334 (1972), S. 279-292 
    ISSN: 1432-2013
    Keywords: Insulin ; Iodoacetate ; Glycolysis ; Muscle Metabolism ; Carbohydrate Metabolism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1,2-Bisphosphoenolpyruvate (bis-PEP), a new intermediate of carbohydrate metabolism, accumulates in the incubation medium of rat diaphragms. The metabolic properties of this intermediate have been studied. Bis-PEP is determined after isolation, by its radioactivity and the total phosphorus content. The production is stimulated by insulin. The addition of adrenalin and monoiodoacetate to media containing insulin causes a further increase in concentration of bis-PEP in the medium. When incubating with glucose labeled in the first or the sixth carbon atom, the dilution of the isotope incorporated into bis-PEP is different. The use of 1-14C-glucose gives rise to the production of bis-PEP with low specific activity; this dilution is counteracted by the addition of monoiodoacetate to the medium. The addition of non-radioactivedl-glyceraldehyde to the medium causes a doubling of the total amount accumulated and an approximately equal increase in isotope dilution. The addition of inert hydroxypyruvate decreases the dilution factor without increasing the total amount. When glycogen in the diaphragms is labeled by preliminary incubation with14C-glucose, labeled bis-PEP can be isolated from a second, non-radioactive medium. Anaerobiosis does not inhibit production. Assuming that in the intact diaphragm as in isolated systems the effect of monoiodoacetate is first and foremost on glyceraldehydedehyrogenase, it is suggested that the synthesis of bis-PEP takes place at a point above the formation of 1,3-diphosphoglycerate.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Acta diabetologica 9 (1972), S. 540-561 
    ISSN: 1432-5233
    Keywords: Carbohydrates ; Cholesterol ; Fats ; Insulin ; Lipoprotein lipase ; Lipoproteins ; NEFA ; Nicotinic acid ; Pre-β-lipoproteins ; Serum lipids ; Triglycerides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé On a étudé 84 sujets diabétiques a fin de mettre en évidence la frequence et le type des complications hyperlipidémiques au cours de la maladie diabétique. Pour déterminer quelques aspects de la pathogénèse, des patients ont reçu une diète hyperglucidique (CHO 75–80%), des autres ont reçu un surplus diététique de beurre (30% des calories totales), des autres enfin ont été tratés par acide nicotinique (2 g/die pendant 8 jours). Les résultats ont mis en évidence que une hyperlipémie est très fréquente au cours de diabète mais elle jamais atteint à des niveaux élevés; le type II est rare tandis que prédomine le type IV; il y a même la présence de un type «mélangé» (II+IV) e de «sinking pre-β». L'hyperlipémie, caractérisée par une légère réduction de la lipoprotéine-lipase, n'est pas modifiable ni par des diètes hyperglucidiques ni avec le surplus de gras saturés; au contraire l'action de l'acide nicotinique a réduit l'hyperglycémie et la bande pre-β. La légère hyperlipémie habituelle des diabétiques semble causée par une aumentation de l'afflux de NEFA au foie et par un déficit de la rémotion plasmatique de VLDL. Excéptionnellement une «grosse» hyperlipemie complique le diabète de la maturité ou le diabète en acido-cétose; en ces cas il s'agirait plus de une association de plusieurs gènes morbides que de une interdèpendence pathogénétique.
    Abstract: Resumen Los autores han estudiados una serie de 84 diabéticos, al objeto de determinar la frecuencia con que la diabetes se complica con una hiperlipemia y el tipo de esta última. Para determinar algunos aspectos de la patogenesis, una parte de los pacientes se sometió a dieta hiperglucídica (carbohidratos 75–80 %), otra recibió un suplemento dietético de mantequilla (equivalente al 30% de la totalidad de calorías) y, finalmente, otra fue sometida a un tratamiento con ácido nicotínico (2 gramos diarios durante 8 días). Los datos obtenidos han demostrado que la hiperlipemia se da muy frecuentemente durante la diabetes pero que habitualmente no alcanza grados elevados; el tipo II se da con escasa frecuencia; predomina el tipo IV de hiperlipoproteinemia; y también se da la presencia de un tipo «mixto» y en un cierto porcentaje figuran también las «sinking pre-β». La hiperlipemia, caracterizada preferentemente por una leve reducción de la lipoproteinlipasa, no ha resultado susceptible de modificaciones ni con la dieta hiperglucídica ni con el suplemento de grasas saturadas; en cambio, tanto la hiperglicemia como lafaja pre-β se ha atenuado bajo el tratamiento con ácido nicotínico. La leve hiperlipemia habitual del diabético parece pues que se vincule a una hiperafluencia de NEFA al hígado y a un déficit de la eliminación plasmática de VLDL. En casos excepcionales una «gran» hiperlipemia complica la diabetes de la madurez o la diabetes quetonúrica; en tales casos más que una interdependencia patogenética parece que lo que está en juego es una asociación de genes morbosos plúrimos.
    Notes: Riassunto Gli AA. hanno studiato una serie di 84 diabetici, al fine di accertare la frequenza con cui il diabete si complica con una iperlipemia, nonché il tipo di questa. Per determinare alcuni aspetti della patogenesi, parte dei pazienti sono stati sottoposti a dieta iperglicidica (carboidrati 75–80 %), parte hanno ricevuto un supplemento dietetico di burro (pari al 30 % delle calorie totali), mentre altri sono stati sottoposti a trattamento con acido nicotinico (2 g/die per 8 giorni). I dati ottenuti hanno consentito di accertare come una iperlipemia sia molto frequente in corso di diabete, ma come essa non raggiunga abitualmente gradi elevati; il tipo II è scarsamente frequente, mentre predomina il tipo IV di iperlipoproteinemia; vi è presenza anche di un tipo «misto», mentre in una certa aliquota figurano anche le «sinking pre-β». L'iperlipemia, per lo più caratterizzata da una lieve riduzione della lipoprotein-lipasi, non è risultata modificabile né con la dieta iperglicidica né con il supplemento di grassi saturi; sia l'iperlipemia che la banda pre-β si sono invece attenuate sotto trattamento con acido nicotinico. La lieve iperlipemia abituale del diabetico sembra quindi legata a un iperafflusso di NEFA al fegato e a un deficit della rimozione plasmatica di VLDL. In casi eccezionali, una «grossa» iperlipemia complica il diabete della maturità o il diabete chetonurico; in questi casi, più che una interdipendenza patogenetica sembra in gioco l'associazione di geni morbosi plurimi.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Acta diabetologica 9 (1972), S. 900-923 
    ISSN: 1432-5233
    Keywords: Fat cells ; Glucose uptake ; Insulin ; Kinetic constants ; Rat epididymal tissue ; Second order kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Après avoir mesuré le captage de glucose par les adipocytes de rat, on calcule les valeurs de K (constante de semi-saturation) et de V (captage maximum à des concentrations de glucose saturantes). L'insuline accroît le captage de glucose, tandis que le mannose et le 3-O-méthylglucose l'interdisent. Plusieurs préparations cellulaires donnent des valeurs différentes en ce qui concerne K, V et la sensibilité à l'insuline. On prend en considération l'effet possible de la teneur en triglycérides des adipocytes sur ces différents paramètres. Cependant, le caractère non-linéaire de certains diagrammes où les deux variables sont transformées dans leurs valéurs réciproques et certaines corrélations entre les divers paramètres cinétiques laissent penser à deux systèmes de captage de glucose dans les adipocytes de rat.
    Abstract: Resumen Se calculan los valores de K (constante de semisaturación) y de V (captación máxima y concentraciones de glucosa saturantes), por medio de mediciones de la captación de glucosa por parte de adipocitos de rata. La insulina aumenta la captación de glucosa, mientras que la manosa y el 3-O-metilglucosa la inhiben. Preparados celulares diversos facilitan diferentes valores por lo que se refiere a K, V y la sensibilidad a la insulina. Se considera el posible efecto del contenido de triglicéridos de los adipocitos según esos diversos parámetros. Sin embargo, la falta de linealidad de algunos diagrams en los que las variables se han transformado en sus recíprocos y ciertas correlaciones entre los varios parámetros cinéticos dan lugar a que se pueda suponer que en los adipocitos de rata puedan existir dos sistemas de captación de la glucosa.
    Notes: Riassunto Da misurazioni della captazione di glucosio da parte di adipociti di ratto vengono calcolati i valori di K (costante di semi-saturazione) e di V (captazione massima a concentrazioni di glucosio saturanti). L'insulina aumenta la captazione di glucosio, mentre il mannosio ed il 3-O-metilglucosio la inibiscono. Preparati cellulari diversi forniscono differenti valori per quanto riguarda K, V e la sensibilità all'insulina. Viene considerato il possibile effetto del contenuto in trigliceridi degli adipociti su questi diversi parametri. Tuttavia, la non linearità di alcuni diagrammi in cui entrambe le variabili sono trasformate nei loro reciproci e certe correlazioni tra i varî parametri cinetici fanno pensare che negli adipociti di ratto possano esserci due sistemi di captazione del glucosio.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Acta diabetologica 9 (1972), S. 865-899 
    ISSN: 1432-5233
    Keywords: cAMP ; Chlorpropamide ; Diabetes ; Glibenclamide ; Glibornuride ; Glucagon ; Insulin ; Methylxanthines ; Sulphonylureas ; Tolbutamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé A présent, il est certain que les sulfanilurées exerçent essentiellement leur action au niveau du pancréas, stimulant la sécrétion insulinique et interdisant la sécrétion du glucagone. Dès la découverte des substances hypoglycemisantes par la voie orale, le développement de nouvelles sulfanilurées encore plus fortes a fait l'objet d'un très vif intérêt. Tout récemment, par la synthèse d'un nouveau composé plus puissant appartenant au groupe des sulfanilurées — la glibenclamide (HB 419, Daonil®) —, des progrès encourageants ont été réalisés, notamment en ce qui concerne le traitment du diabète chez les individus d'un âge mûr. Nombre de patients dépendant de l'insuline atteints de cette forme de diabète peuvent être traités en effet avec de la glibenclamide. Parfois, il se peut que des hypoglycemies masquées se manifestent, ce qui témoigne de l'activité intense de cette substance. La glibenclamide se diversifie des autres sulfanilurées du fait des différentes modalités qui provoquent la sécrétion d'insuline. Cette substance agit également synergiquement avec le glucose stimulant cette sécrétion. Aucun autre médicament hypoglycemisant ne permet, chez l'animal aussi bien que chez l'homme, d'accroître dans une mesure autant considérable la tolérance des glycides. La glibenclamide semble exercer son influence au niveau de la cellule B sur le même récepteur ou avec le même mécanisme agissant avec le glucose.
    Abstract: Resumen Actualmente se considera como un hecho cierto que las sulfanilureas actúan principalmente a nivel del áncreas estimulando la secreción insulínica e inhibendo la de glucagón. Desde la época en que fueron descubiertas las substancias hipoglicémicas orales, ha sido objeto de vivo interés el desarrollo de sulfanilureas nuevas y más potentes. Recientemente, a través de la síntesis de un compuesto muy potente perteneciente al grupo de las sulfanilureas — la glibenclamida (HB 419, Daonil®) —, se han realizado progresos alentadores sobre todo en el tratamiento de la diabetes de la edad madura. En efecto, muchos enfermos insulinodependientes afectos de dicho tipo de diabetes pueden pasar a la glibenclamida. A veces se pueden virificar hipoglicemias disfrazadas, que prueban la intensa actividad de esta substancia. La glibenclamida se diferencia de las demás sulfanilureas por las diversas modalidades con que provoca la secreción de insulina. Además, actúa sinérgicamente con la glucosa en el stímulo de dicha secreción. Ningún otro producto hipoglicémico es capaz, tanto en el hombre como en el animal, de aumentar en medida tan notable la tolerancia glucídica. La glibenclamida parace actuar a nivel de la célula B en el mismo receptor o con el mismo mecanismo con que actúa la glucosa.
    Notes: Riassunto Attualmente, è considerato un fatto certo che le sulfaniluree agiscano principalmente a livello del pancreas, stimolando la secrezione insulinica ed inibendo quella del glucagone. Sin dall'epoca della scoperta degli ipoglicemizzanti orali, lo sviluppo di nuove e più efficaci sulfaniluree è stato oggetto di vivo interesse. Recentemente, attraverso la sintesi di un nuovo ed assai efficace composto appartenente al gruppo delle sulfaniluree — la glibenclamide (HB 419, Daonil®) —, incoraggianti progressi sono stati compiuti, soprattutto nel trattamento del diabete dell'età matura. Molti pazienti insulino-dipendenti affetti da tale tipo di diabete possono essere infatti passati alla glibenclamide. Talvolta possono verificarsi ipoglicemie mascherate, a dimostrazione dell'intensa attività di questa sostanza. La glibenclamide si differenzia dalle altre sulfaniluree per le diverse modalità con cui provoca la secrezione di insulina. Essa agisce inoltre sinergicamente con il glucosio nello stimolare tale secrezione. Nessun altro farmaco ipoglicemizzante è capace, sia nell'animale che nell'uomo, di aumentare in misura altrettanto notevole la tolleranza glicidica. La glibenclamide sembra agire a livello della cellula B sullo stesso recettore o con il medesimo meccanismo con cui agisce il glucosio.
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  • 12
    Electronic Resource
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    Springer
    Acta diabetologica 9 (1972), S. 299-304 
    ISSN: 1432-5233
    Keywords: Complex formation ; Cysteine ; Cystine ; Insulin ; Tryptophan
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Par la méthode chromatographique de la gel-filtration sous les mêmes conditions réalisées pour l'isolement du complexe insuline tryptophane, aucune formation de complexes avec cysteine et cystine n'a été vérifiée.
    Abstract: Resumen Empleando el método cromatográfico da la gel-filtración, en las mismas condiciones actuadas para el aislamiento del complejo insulina-triptófano, no se ha observado formación de complejos con la cisteina y la cistina.
    Notes: Riassunto Impiegando il metodo cromatografico della gel-filtrazione, nelle medesime condizioni attuate per l'isolamento del complesso insulina-triptofano, non è stata osservata formazione di complessi con la cisteina e la cistina.
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  • 13
    ISSN: 1432-5233
    Keywords: Adipose tissue ; Antilipolytic effect ; Glycerol release ; Insulin ; Isolated fat cells ; Norepinephrine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Les Auteurs ont étudié l'effet antilypolytique de l'insuline sur la lypolyse induite par la noradrénaline. Après avoir choisi une dose minime d'hormone capable d'exercer sûrement une action antilypolytique, les Auteurs ont comparé des insulines de type différent, y compris l'insuline humaine, afin de déterminer l'existence éventuelle d'une efficacité différente.
    Abstract: Resumen Los autores han estudiato el efecto antilipolítico de la insulina sobre la lipolisis inducida por la noradrenalina. Tras haber elegido una dosis mínima de hormón capaz de desarrollar una acción antilipolítica segura, los autores han comparado entre ellas insulinas de diferentes especies, incluso de la humana, con la finalidad de determinar la posible existencia de una diversa eficacia.
    Notes: Riassunto Gli AA. hanno studiato l'effetto antilipolitico dell'insulina sulla lipolisi indotta dalla noradrenalina. Dopo aver scelto una dose minima di ormone capace di esercitare una sicura azione antilipolitica, gli AA. hanno confrontato tra loro insuline di specie differente, compresa quella umana, allo scopo di determinare l'eventuale esistenza di una diversa efficacia.
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  • 14
    Electronic Resource
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    Springer
    Acta diabetologica 9 (1972), S. 15-45 
    ISSN: 1432-5233
    Keywords: Biological activity ; Connecting-peptide (C-peptide) ; Diabetes ; Functioning islet cell tumor ; Immunological activity ; Insulin ; Obesity ; Proinsulin ; Serum C-peptide ; Serum proinsulinlike material
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé La molécule de la proinsuline, precurseur à chaîne unique de l'insuline, commence par la chaîne B de l'insuline, continue à travers un peptide contenant quelque 30–35 acides aminés, par rapport à l'espèce, et se termine par la chaîne A de l'insuline. De nombreuses enquêtes expérimentalesin vitro ont révélé que la transformation de la proinsuline en insuline est liée à la formation des granules de sécrétion et que le C-peptide n'est pas métabolisé à l'intérieur des cellules B. Il a été démontré que la proinsuline et le C-peptide sont présents dans le sérum de sujets normaux, obèses et diabétiques. A jeun, la concentration de la proinsuline sérique représente environ 40 % de celle de l'insuline (c'est-à-dire 25 % de l'IRI sérique totale). Après une administration de 100 grammes de glucose, on a observé une diminution du rapport proinsuline/insuline. Dans quelques sujets ayant une tumeur fonctionnante des îlots de Langerhans, les valeurs de la proinsuline peuvent être extrêmement élevées, jusqu'à représenter environ 80–90 % de l'IRI sérique. La détermination du C-peptide dans le sérum a été effectuée par une méthode radioimmunologique spécifique. Après glucose, on a observé une augmentation des valeurs sériques du C-peptide. Dans des sujets normaux, obès et diabétiques et dans des sujets avec insulinome, les valeurs sériques du C-peptide et de l'insuline étaient essentiellement équivalents, si elles étaient évaluées sur base molaire. La présence de la proinsuline et du C-peptide dans la circulation a suscité un interêt considérable pour un effet éventuel biologique de ces substances. En dépit des résultats contrastants concernant l'activité biologique de la proinsuline, probablement à cause des techniques différentes utilisées, les effets métaboliques de la proinsuline dans les différents tissus sont très semblables à ceux de l'insuline. Par contre, le C-peptide ne semble pas posséder d'activité biologique. Il n'est pas encore certain si la proinsuline et le C-peptide présents dans la circulation exercent quelque action spécifique au niveau des tissus périphériques ou bien s'ils représentent simplement une conséquence passive du mécanisme de sécrétion de l'insuline.
    Abstract: Resumen La molécula de la proinsulina, precursora en cadena única de la insulina, inicia con la cadena B de la insulina, continua a través de un péptido compuesto de unos 30–35 aminoácidos, en relación con la especie y termina con la cadena A de la insulina. Numerosas investigaciones experimentalesin vitro sugieren que la transformación de la proinsulina en insulina se vincula a la formación de los gránulos de secreción y que el C-péptido no se metaboliza dentro de las células B. Se ha demostrado que la proinsulina y el C-péptido se hallan presentes en el suero de individuos normales, obesos y diabéticos. En ayunas, la concentración de la proinsulina serosa alcanza el 40 % aproximadamente de la correspondiente a la insulina (es decir, el 25 % del IRI sérico total). Tras suministro de 100 gramos de glucosa se ha observado una disminución de la relación proinsulina/insulina. En algunos individuos con tumor activo en las islas de Langerhans, los valores de la proinsulinemia pueden llegar a ser muy elevados, hasta alcanzar casi el 80–90 % del IRI suerosa. La determinación del C-péptido en el suero se ha efectuado por medio de un método radioinmunológico específico. Tras glucosa se ha observado un aumento de los valores suerosos del C-péptido. En individuos normales, obesos y diabéticos y en individuos con insulinoma los valores suerosos del C-péptido en circulación ha suscitado notable interés bajo el aspecto de un posible efecto biológico de esas substancias. A pesar de que con respecto a la actividad biológica de la proinsulina los resultados se presentan más bien en contraste, probablemente en función de las diversas técnicas seguidas, los efectos metabólicos de la proinsulina en los varios tejidos son muy parecidos a los de la insulina. Por el contrario, el C-péptido no parece tener actividad biológica alguna. Todavía no se conoce con seguridad si la proinsulina y el C-péptido presentes en la circulación desarrollan alguna función espécifica a nivel de los tejidos periféricos o si simplemente son una consecuencia pasiva del mecanismo de secreción de la insulina.
    Notes: Riassunto La molecola della proinsulina, precursore a catena unica dell'insulina, inizia con la catena B dell'insulina, prosegue attraverso un peptide composto di circa 30–35 aminoacidi, in rapporto alla specie e termina con la catena A dell'insulina. Numerose indagini sperimentaliin vitro suggeriscono che la trasformazione della proinsulina in insulina sia legata alla formazione dei granuli di secrezione e che il C-peptide non venga metabolizzato all'interno delle cellule B. É stato dimostrato che la proinsulina e il C-peptide sono presenti nel siero di soggetti normali, obesi e diabetici. A digiuno, la concentrazione della proinsulina sierica rappresenta circa il 40 % di quella dell'insulina (ovvero circa il 25 % dell'IRI sierica totale). Dopo somministrazione di 100 g di glucosio, è stata osservata una diminuzione del rapporto proinsulina/insulina. In alcuni soggetti con tumore funzionante delle isole di Langerhans, i valori della proinsulinemia possono essere molto elevati, fino a rappresentare circa l'80–90 % dell'IRI sierica. La determinazione del C-peptide nel siero è stata eseguita per mezzo di un metodo radioimmunologico specifico. Dopo glucosio, è stato osservato un aumento dei valori sierici del C-peptide. In soggetti normali, obesi e diabetici e in soggetti con insulinoma i valori sierici del C-peptide e dell'insulina erano essenzialmente equivalenti se valutati su base molare. La presenza della proinsulina e del C-peptide in circolo ha suscitato notevole interesse nei riguardi di un eventuale effetto biologico di queste sostanze. Nonostante che nei riguardi dell'attività biologica della proinsulina i risultati siano piuttosto contrastanti, probabilmente in rapporto alle diverse tecniche impiegate, gli effetti metabolici della proinsulina nei varî tessuti sono molto simili a quelli dell'insulina. Al contrario, il C-peptide non sembra possedere alcuna attività biologica. Non è ancora certo se la proinsulina e il C-peptide presenti in circolo svolgano qualche funzione specifica a livello dei tessuti periferici oppure se essi rappresentino semplicemente una conseguenza passiva del meccanismo di secrezione dell'insulina.
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  • 15
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simplified scheme for treating the spatial configurations of polynucleotide chains is developed using the rotational isomeric state approximation and statistical methods applicable to linear systems of interacting subunits. As a consequence of geometric constraints imposed by the skeletal structure and of the severity of certain steric interactions, it is possible to represent the repeat unit comprising six skeletal bonds by two virtual bonds of fixed length. The configuration of the polynucleotide chain as a whole may be conveniently described by an alternating succession of these two virtual bonds. Moreover, analysis of steric interactions suggests that bond rotations governing the mutual orientation of a given pair of successive virtual bonds should be sensibly independent of the rotations affecting the mutual orientation of other pairs. The statistical mechanical treatment of configuration-dependent properties is much simplified in consequence of this mutual independence. Mean-square dimensions calculated by giving equal weights to all sterically allowed conformations are much smaller than values determined by Felsenfeld and co-workers. The calculated dimensions are markedly increased, however, by placing certain arbitrary restrictions on the rotations about selected pairs of skeletal bonds. It is thus demonstrated that steric interactions alone are insufficient to account for the spatial characteristics of polynucleotide chains. The dimensions are also found to be sensitive to the conformation of the ribose ring of each nucleotide unit, but, insofar as the influences of steric interactions are concerned, the dimensions do not depend on the heterocyclic base attached to the ribose ring.
    Additional Material: 6 Ill.
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  • 16
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    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 119-126 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theory is presented concerning the possible arrangements of protomers in tetrameric molecules. Isoenzymes may exist even in the case of homotetramers if the asymmetry of the identical protomers is detectable. The number of tetrahedral isoenzymes that can be isolated depends on the nature of the intersubunit bonds and on the level of the asymmetry of the protomers. Five isoenzymes can be distinguished only if two different types of protomers form tetrahedral tetramers and the asymmetry of protomers is not detectable with the method used. If the two types of protomers can bind each other by any pairs of binding sets and the asymmetry of both protomer types reaches the level of detection with the method used, we obtain 117 isoenzymes: 15 individual ones, and 51 stereoisomeric pairs.
    Additional Material: 3 Tab.
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  • 17
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    Biopolymers 11 (1972), S. 197-214 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Our previous paper described graphical procedures for evaluating the mode of association in ideal discrete and indefinite cases. This paper concerns the application of such procedures in cases where the non-ideality term BM1 must be considered. Bovine liver L-glutamate dehydrogenase and lysozyme are used as model systems. Several graphical procedures for dealing with cases of 1 - m, 1 - m - n, or indefinite association are developed. The procedure is based on the evaluation of the weight-fraction monomer with-out prior calculation of BM1, using graphical analysis to evaluate the non-ideality term.
    Additional Material: 4 Ill.
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  • 18
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    Biopolymers 11 (1972), S. 271-278 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 6 Ill.
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  • 19
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of L-lysine peptides (Lysn, n = 2-14) from polyL-lysine is described. Fractionation by ion-exchange column chromatography of poly-L-lysine hydrolysates on a preparative scale resulted in 0.2-1.0 g quantities of individual members of the poly-L-lysine series. The peptides isolated proved to be analytically pure and the optical configuration was fully retained, as demonstrated by complete enzymic digestion. Peptides higher than n = 14 were also prepared. They consisted of oligolysine groups of narrow and accurately determined size distribution. Potentiometric titrations were used both to characterize the products and to demonstrate the characteristic dependence of the dissociation constants on size of the peptide.
    Additional Material: 11 Ill.
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  • 20
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    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 549-561 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of double helix formation by single stranded Poly A plus Poly U, Poly I plus Poly C, Poly G plus Poly C, and T2 DNA has been investigated as a function of both the length of the reacting strands and temperature. The length dependence of the rate is found to be independent of temperature. All of the reactions studied show a rate approximately proportional to the square root of the length of the shorter of the complementary strands. At or about 30°C below the melting temperature the ribopolymers react with about the same rate. This rate is four to five times slower than DNA renaturation rates. The effect of temperature on ribopolymer reaction rates is interpreted in terms of a steady-state model for helix propagation.
    Additional Material: 6 Ill.
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  • 21
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    Biopolymers 11 (1972), S. 653-659 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: NMR spectra of cyclo(tri-L-prolyl), c-(P)3, show large shifts of the Hα resonance on adding C6D6 to a solution of c-(P)3 in CD2Cl2. CPK models and observed coupling constants indicate a rigid c-(P)3 conformation, independent of solvent composition, suggesting that these shifts result from formation of stereospecific C6D6-c-(P)3 collision complexes in which the c-(P)3 Hα lie near the face of the aromatic ring. The temperature dependence of the Hα shifts and the solvent dependent shifts observed on adding toluene-d8 or nitrobenzene-d5 to the c-(P)3 solution suggest that preferred C6D6-c-(P)3 orientations result from attractive interactions between the electron-rich aromatic ring and the electropositive Hα's and/or δ+ nitrogen atoms in the peptide backbone. Reports of such interactions in increasingly diverse peptide model systems suggest that they may play a role in stabilizing protein structures.
    Additional Material: 2 Ill.
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  • 22
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 835-847 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal denaturation of native or partially dehistonized nucleohistones shows two melting bands at 66 and 81° in 2.5 × 10-4 M EDTA, pH 8.0. These correspond to the melting of DNA segments bound by the less basic and the more basic half-molecules of histones, respectively. These two melting bands combine into a broad melting band from around 70 to 85° when these nucleohistones are pre-treated with formaldehyde. A formaldehyde reaction which fixes histones on DNA by covalent bonds account for the effect. Formaldehyde fixation also increases the melting temperature of some free DNA segments from around 42 to around 55°. This is interpreted as a result of closed or rigid boundaries between free DNA and formaldehyde-reacted histone-bound DNA segments. MgCl2 dissociates histones from DNA more effectively and leaves longer free DNA segments than does NaCl. Thermal denaturation of a formaldehyde-reacted nucleoprotein thus provides an effective tool for comparing the relative size of free DNA regions on nucleoproteins. The effect of reversible binding of ligands on helix-coil transition of DNA is descussed and found not adequate for thermal denaturation of nucleohistones.
    Additional Material: 7 Ill.
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  • 23
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    Biopolymers 11 (1972), S. 899-912 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isometric tensile stress generation observed when collagen fibers are immersed in aqueous solutions of lithium bromide ranging in molar concentration up to 7 was studied at 23°C. The reverse process, namely, isometric stress relaxation of the fiber occurring by subsequent immersion in distilled water, was also studied. We find that the data in the region of LiBr concentration up to about 2.5 moles/liter are adequately represented by a superposition integral \documentclass{article}\pagestyle{empty}\begin{document}$$ \sigma (t) = \int_{ - \infty }^\infty {K(t - \tau )} \frac{{dc(\tau )}}{{d\tau }}\,d\tau $$\end{document} where σ(t) is the time-dependent stress generated by the collagen fiber held at fixed length, c(t) is the history of LiBr molar concentration, and K(t) is the isometric contractility function, expressed as stress per unit salt concentration. We conclude that, within a limited range of salt concentration, a collagen fiber in a LiBr bath behaves as if it were a linear, time-invariant system defined mechanochemically by a single function K(t) which depends on the structural characteristics of the fiber while being independent of salt concentration. An analysis is presented of isometric mechanochemical data obtained under conditions of equilibrium by other workers who studied the behavior of collagen fibers in aqueous solutions either of urea, LiBr, or KCNS. The analysis shows that these independent (equilibrium) data confirm the linarity of the relation between isometric contractile stress and salt concentration on which our superposition integral representation is based. We also find that the asymptotic (infinite-time) value of the isometric stress is linearly related to the chemical potential of the salt as well, in agreement with the equilibrium thermodynamic treatment of mechanochemical processes by Katchalsky and Oplatka.
    Additional Material: 7 Ill.
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  • 24
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 25
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    Biopolymers 11 (1972), S. 937-949 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general theory of polyelectrolyte solutions is here used to calculate the differences in Gibbs free energy, enthalpy, and entropy between the coil and helix forms of DNA at any temperature and salt concentration. The salt has univalent cations and is assumed present in excess over the base concentration. The results are restricted to sufficiently dilute solutions. It is shown that the salt concentrations effect is entirely entropic in origin. When applied to the melting temperature, the calculations yield a relation between the enthalpy difference at the melting temperature and the slope of the plot of melting temperature vs. the logarithm of the salt concentration. In accord with observation, both the Gibbs free energy difference at any fixed temperature and the melting temperature are predicted to be linear functions of the log of the salt concentration.However, the theory is not in quantitative agreement with enthalpy data. Data on various colligative and transport properties of both helix and coil forms are reviewed in the text and in Appendix B, and good agreement is found with theory for both forms. No attempt is made to explain why the theory is quantitative for these properties but not for heat measurements.Finally, in Appendix A, an approximate calculation is made of the free energy contributions due to ionic effects not associated with the salt concentration.
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  • 26
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    Biopolymers 11 (1972), S. 1001-1020 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-molecular-weight poly-L-alanine dissolved in hexafluoroisopropanol exhibits infrared, ultraviolet, circular dichroism, and optical rotatory dispersion spectra which are unique and unlike any other previously reported polypeptide spectra. Strong evidence that a helical conformation is present is shown by the high degree of hypochromism in the 187mμ absorption peak and by the positions of the amide infrared bands. The CD and ORD spectra are also similar to those of α-helical polypeptides, though important qualitative and qualitative differences are observed. To explain the novel spectra, which are not mixtures of the spectra of previously reported polypeptide conformations, a new α-helix-like conformation is proposed. The postulated conformation (a doubly hydrogen-bonded helix) is a distorted α-helix in which the peptide carbonyl groups point slightly out from the helix axis and are hydrogen bonded simul taneously both to the NH of the fourth peptide residue to the carboxyl terminal side (as in the classical α-helix), as well as to a solvent molecule's hydroxyl hydrogen.
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  • 27
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    Biopolymers 11 (1972), S. 1091-1102 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichriosm (CD) spectra have been calculated for serveral dinucleoside phosphates using a variant of the Pariser-Parr-Pople π-electron molecular orbital method. This method does not require the prior knowledge of the experimental absorption spectra of transition moments of the bases forming the dinucleoside phosphates. Calculated spectra were obtained in good agreement with experimental spectra for four dinucleoside phosphates, ApA, UpU, GpA, and UpA, and reasonable agreement was obtained for ApG and ApU. The effect of changing conformation on the CD spectrum was studied for ApA, UpU, UpA, and ApU; the spectra of UpU, UpA, and ApU were sensitive to small change in conformation, whereas ApA was insensitive over the range of conformation studied. Further studies await detailed knowledge of the structure of dinucleoside phosphates in solution.
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  • 28
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    Biopolymers 11 (1972), S. 1259-1268 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solvent-and pH-induced conformational changes are examined in order to investigate the influence of benzyl group. Polymer was prepared via N∊-benzyloxycarbonyl, N∊-benzyl-Nα-carboxy-L-lysine anhydride. The resulting poly (N∊-benzyloxycarbonyl, N∊-benzyl-L-lysine) was obtained in high yield and had a high molecular weight. The protected polymer was removed into poly (N∊-benzyl-L-lysine) by treating it with hydrogen bromide. From the results of the ORD and CD, the protected polymer has a righthanded α-helix, showing [m′]233 = -10,300, [θ]220 = -27,600 and [θ]207 = -25,100 in dioxane. The breakdown of the helical conformation is found to occur at 8% dichloroacetic acid in chloroform-dichloroacetic acid mixture. In the pH range 3.35-6.90, poly (N∊-benzyl-L-lysine) is in a random coil structure. In the pH range 7.50-13.0, the polypeptide has a right-handed α-helix structure; [m′]233 = -12,000, [0]220 = -27,200, and [0]207 = -27,000. In comparison with poly-L-lysine, the coil-to-helix transition is observed at lower pH range in 50% n-propanol. Above pH 8 by heating, the α ⇀ β transition of poly (N∊-benzyl-L-lysine) is not observed in an aqueous media.
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  • 29
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    Biopolymers 11 (1972), S. 1305-1310 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 30
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    Biopolymers 11 (1972), S. 1499-1520 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple sequential model is developed which is applicable to the kinetics of melting of some types of oligomeric helices and as an idealization to the kinetics of unfolding of some protein molecules. A procedure is presented for calculating the concentrations of all conformational species as functions of time. The time course of experimentally observable quantities which depend on these concentrations may then be computed.One of the most characteristic features of the model is the distinction between a transient and a steady-state phase. During the latter all molecular parameters change at the same rate, which depends strongly on the difficulty of nucleation and the length of the sequence. Simple approximations to the steady-state rate are discussed in terms of the exact solution. Rates of transient processes dependless strongly on the rate of nucleation and the number of steps and are a more direct reflection of the rates of the rates of the elementary process of propagation. The value of experimental observation of transient process is emphasized.
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  • 31
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    Biopolymers 11 (1972) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 32
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    Biopolymers 11 (1972), S. 1593-1605 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Far-infrared spectra were measured for the sequential copolymers of amino acids with alkyl group side chains. The analysis of the spectra showed that (L-Ala-L-Ala-Gly)n, (L-Ala-Gly)n, (L-Ala-Gly-Gly)n, (L-Val-L-Ala-L-Ala)n, and (L-Val-L-Ala)n, have the antiparallel pleated sheet structures and that the backbone conformations of (L-Val-L-Val-L-Ala)n and (L-Val-L-Val-Gly)n are the same as that of poly-L-valine. The far-infrared bands characteristic of the antiparallel pleated sheet structure were assigned on the basis of the result of the normal coordinate analysis of poly-L-alanine with this structure. The intersheet and interchain spacings of the sequential copolymers with the antiparallel pleated sheet structure were determined from the x-ray powder-diffraction patterns of these samples.
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  • 33
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    Biopolymers 11 (1972), S. 1583-1592 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichroism spectra of acridine orange bound to E. coli tRNA were studied at varying tRNA phosphate-to-dye (P/D) ratios for both unfractionated and purified materials in the absence of Mg++. From the rather discrete features exhibited in the circular dichroism spectra three types of interactions were observed: (1) A high P/D ratio such as 75.2 or 49.8 indicates the interaction between the nucleotide base and dye molecule. The spectra with a large positive peak at 515 mμ are, however, quite different from that of DNA-AO complex under similar conditions. (2) With an intermediate P/D ratio (26.5 to 9.6) dye molecules bound strongly to the polynucleotide chain. (3) With low P/D ratios (≤7.5) the interaction appears to be due to the stacked dye molecules in the single-stranded part of tRNA. The spectra of the third group have an isobestic point at 477 mμ. Below a P/D ratio of 4 the spectrum shows one positive and two negative bands which may be the characteristics of circular dichroism of stacked dyes in polynucleotide chain.Although no drastic change in the conformation of tRNA itself was detectable in the presence of Mg++ in the ultraviolet region, a dramatic change was observed in the circular dichroism of tRNA-acridine orange complex when Mg++ concentration was increased to 10-3M. It was inferred that certain conformational changes other than simple hydrogen bond formation occured in tRNA molecules at this high Mg++ concentration, so that the amount of bound dye in the stacking condition was increased through the transition.
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  • 34
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    Biopolymers 11 (1972), S. 1607-1612 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly (L-Prolyl-Glycyl-L-Prolyl), a polymer which resembles collagen by physical and immunochemical criteria, has been shown to serve as a substrate for the highly specific bacterial collagenase obtained from Clostridium histolyticum. The postulated reaction products Gly Pro, Gly Pro Pro, and Pro Gly Pro Pro have been isolated. The enzyme has been employed as an analytical tool in elucidating the sequence of synthesized polymers of proline and glycine.
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  • 35
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Apparent second-order rate constants for complex formation between poly (I) and poly (C) and copolymers of C containing non-complementary I or U residues have been determined spectrophotometrically. The rate constants decrease as the concentration of either I or U in the C strands increases-the effect seems insensitive to the species of residue involved, when differences in the thermal stabilities of the poly (I) poly (C,I) and poly (I). poly (C,U) complexes are taken into account. These results suggest that low concentrations of relatively stable defects can alter the apparent kinetic “complexity” of polynucleotides as determined by hybridization methods (C0t analysis).
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  • 36
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    Biopolymers 11 (1972), S. 1661-1684 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DNA which has been heat denatured in the presence of Cu++ ions can be completely and rapidly renatured by increasing the ionic strength of the solution above a critical value. A kinetic study of this renaturation recation was carried out by following the associated UV absorbance change and also by following the change in free Cu++ ion concentration by means of a specific Cu++ ion activity electrode. The data obtained could be fitted to first-order kinetics for a considerable extent of the reaction and the rate constant was found to increase with temperature and ionic strength, but to decrease markedly as the bulk viscosity of the solution was increased. At temperatures greater than 5°C the reaction rate depended on the time elapsing between denaturation and the commencement of the renaturation reaction. As there was good agreement between the rate constants obtained by following the decrease in hyperchromism and by following the increase in free Cu++ ion concentration, it is concluded that under the conditions employed, the rate of renaturation is determined by the rate of release of Cu++ ions from the denatured DNA-Cu++ complex.
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  • 37
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    Biopolymers 11 (1972), S. 1723-1744 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational aspects of a series of copolymers of L-Leucine and L-leucine [poly-(LysxLeuy)] containing 0 to 0.41 mole fraction L-leucine have been studied by circular dichroism (CD) and potentiometric titration in 0.05M KF solution. CD studies on the α-helical conformation showed a dependence of the magnitude of the CD ellipticity band at 222 nm on copolymer composition; the [θ]222 decreasing with higher leucine contents. This was interpreted as the result of an increase of the hydrophobicity of the environment of the amide group due to the presence of the leucyl residues. Values of the Zimm-Rice parameter, σ, for the copolymers were obtained from the potentiometric titrations and used to fit theoretical curves to the experimental data. Using the variation of σ with polymer composition, a value of σ for the leucyl residue was estimated to be 6.3 × 10-2, assuming independence of σ on the amino acid sequence in the copolymer. The free energy change for the conversion of one mole residue from uncharged helix to uncharged coil, ΔGhc°, was also obtained from the titration data for each copolymer up to a leucine mole fraction of 0.16; a value of 385 cal mole-1 was estimated for ΔGhc° for a leucyl residue. These values for σ and ΔGhc° are compared with other values in the literature for various amino acid residues obtained from titration and melting curve data.
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  • 38
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    Biopolymers 11 (1972), S. 1745-1763 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical rotatory dispersion measurements were used to follow the transition from the helical to the random coil conformation of poly-β-benzyl-L-aspartate as induced by changes in temperature and solvent composition in mixtures of dioxane and dimethylsulfoxide. Within experimental error, there is no difference in the stability of the helical state as measured in this way for the protonated and deuterated forms of the polypeptide. This result is considered in terms of previous attempts to study the isotope effect on conformational transitions of helical biological macromolecules and polypeptides. The conclusion is drawn that the apparent changes in conformational stability observed in these previous systems arise from alteration of the properties of the solvent. Speculations are advanced regarding the contribution of the interpeptide bond to the stability of the helical state.
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  • 39
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    Topics: Chemistry and Pharmacology
    Notes: The helical structures of poly[(S)-thiazolidine-4-carboxylic acid], in the cis and trans forms, were redetermined by using the new sets of bond angles and bond lengths established by X-ray diffraction analysis of L-thioproline. Calculations of the helical structures of poly-L-proline and poly[(S)-oxazolidine-4-carboxylic acid] were also repeated. As a result of these energy calculations, it is suggested that, in contrast to poly-L-proline and poly[(S)-oxazolidine-4-carboxylic acid], poly[(S)-thiazolidine-4-carboxylic acid] should not mutarotate from the trans to the cis form. This result is due to the fact that the energy barrier for the conversion is most likely too high. Previous experimental work is consistent with this finding.
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  • 40
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of optical rotatory dispersion (ORD) and circular dichroism (CD) were made in the range of 400-205 nm for polysaccharide tribenzoates such as 2,3,6-tri-O-benzoyl amylose (I), 2,3,4-tri-O-benzoyl dextran (II), tri-O-benzoyl pullulan (III), 2,3,6-tri-O-benzoyl cellulose (IV), 2,3,6-tri-O-benzoyl mannan (V), and polyglycan dibenzoates such as 2,3,-di-O-benzoyl amylose (VI), cellulose (VII), and mannan (VIII). All compounds exhibit Cotton effects in the region of their UV absorption bands (206-285 nm).Comparison of the corresponding di- and tribenzoyl polysaccharides shows a qualitative agreement in number, position and sign of the CD bands but differences in ellipticity magnitude. The disubstituted derivatives exhibit smaller amplitudes than the trisubstituted ones. The contribution of the C(6) chromophore (linked by a CH2-group to the asymmetric C(5) atom) was determined to be of the same sign as the combined contribution of the C(2) and C(3) substituents.The CD bonds of the individual polysaccharide derivatives, which differ in number, sign, and position, were discussed in terms of the steric position of the single chromophores and the steric arrangement and interaction caused by the configuration of the polysaccharides. The optical behavior of these polysaccharide derivatives was found to be not strongly influenced by a definite chain conformation in solution.
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  • 41
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of the substituents upon the Amide I and νNH frequencies has been analyzed for ten amides substituted by aliphatic side chains. By considering the aliphatic chain field effect, some data are obtained as to the conformation of the N—Cα bond. In two amides, the presence of an equilibrium between two conformers is shown and a semiquantitative estimation of the energies involved is obtained. The consequences for polypeptides conformation, especially for poly-L-valine, are discussed.
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  • 42
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    Biopolymers 11 (1972), S. 2079-2090 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of dielectric constant (D) of the solvent on the viscosity of heparin was examined using the relation \documentclass{article}\pagestyle{empty}\begin{document}$ \eta _{{\rm sp}} /c = [\eta ]_\infty (1 + k/\sqrt c) $\end{document}, where [η]∞ is the shielded intrinsic viscosity obtained by extrapolating \documentclass{article}\pagestyle{empty}\begin{document}$ \eta _{{\rm sp}} /c\,{\rm vs}{\rm . }\,1/\sqrt c ) $\end{document} to infinite concentration, and k is an interaction parameter independent of the dielectric constant of the solvent. This equation was previously reported by the authors9 for describing the reduced viscosities of strong polyelectrolytes in salt-free polar solvents. It was found that the [η]∞ of heparin increases linearly with increasing dielectric constant of the solvent whereas the k values were, within experimental error, independent of D in the range 54.7 〈 D 〈 93.2 examined. Graded hydrolysis of heparin from its acid form (heparinic acid) at 57°C resulted in samples of varying degree of desulfation with corresponding decrease in biological activity. It was found that both [η]∞ and k decrease with increasing desulfation.
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  • 43
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    Biopolymers 11 (1972), S. 2171-2177 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Density gradient analysis of purified lambda phage particles after storage reveals that minor species with new banding desities arise during storage. These have densities expected for phage-ghost clusters containing integra rations of ghosts to phage particles. A lage numbersof new banding species has been observed.
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  • 44
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    Biopolymers 11 (1972), S. 2191-2194 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 45
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    Biopolymers 11 (1972), S. 2223-2231 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The high-humidity X-ray pattern of oriented fibers prepared from salmon spermheads strongly resembles that of DNA in the B form. However, the nucleoprotamine pattern has a more intense first layer line and increased lateral unit-cell dimensions.Complexes of DNA with poly-L-lysine and poly-L-arginine were prepared and photographed at various relative humidities. The most crystalline patterns were obtained at 92% and also indicate DNA in the B form. However, whereas polylysine-DNA, like the spermheads, has a primitive hexagonal cell, polyarginine-DNA, like NaDNA, has three molecules in the unit cell. Polylysine-DNA, but not polyarginine-DNA, also resembles spermheads in having a strong first layer line.All three complexes show increasing intermolecular distance with increasing humidity, but with sharp maxima when photographed in water, which indicates cross-linking between the molecules. Lowering the humidity causes the polylysine-DNA, but not polyarginine-DNA, to change conformation from the B to the C form.The structural implications of these results are discussed in the light of model-building studies and a comparison of calculated and observed X-ray intensities.
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  • 46
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    Biopolymers 11 (1972), S. 2233-2240 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pH, temperature, and reagent concentration dependences of the cyanuration of tyrosines within proteins are compared with those of the free amino acid. The results indicate that the mechanism of the cyanuration reaction is a nucleophilic aromatic substitution of the SN2 type, where the tyrosine oxygen acts as a nucleophile and the displacement takes places at a carbon atom which is part of the six-membered ring of the s-triazene. This reaction must compete with the hydrolysis of cyanuric fluoride in aqueous media. These competing reactions generate curves for the pH dependence of the reactivity of tyrosine with cyanuric fluoride whihc vary in a predictable manner with the extent of ionization of tyrosine and the concentration of cyanuric fluoride. In the case of proteins, the dependence of the degree of tyrosine reactivity on pH and temperature within the pH range of full reactivity of the free amino acid reflects constraints imposed by the microenvironment of these groups within the three-dimensional structure of the macromolecule.
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  • 47
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    Biopolymers 11 (1972), S. 2197-2221 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Serum albumin undergoes a conformational change at pH 4, known as the N-F transition. In the customary Linderstrøm-Lang treatment of hydrogen ion titration, the carboxyl groups in serum albumin either have an abnormally low pK, or are buried in charged form, and the Linderstrøm-Lang charging parameter ω decreases dramatically at the N-F isomerization. In the present paper partition functions are derived and distribution functions are calculated for a model permitting salt bonding between the positively and negatively charged sites on a macromolecule. The N-form has an abnormally high salt bonding constant whereas that of the F-form corresponds to that of small ions. The result obtained is consistent with a “normal” intrinsic pK of the carboxyl groups of serum albumin without burying of any charges and with an unchanged ω. The nature of the postulated salt bonding is discussed.Further, it is shown that the “abnormal salt bonding” of serum albumin can explain its unusual ability to bind anions. Theoretical binding curves are calculated and compared with literature data of the Cl- binding of serum albumin. The relation of the present model to other models of hydrogen ion and anion binding to proteins is discussed. Some additional consequences of the present model are pointed out; a transition in the alkaline range, analogous to the acid transition, seems probable. Literature data support the existence of such a transition but do not allow detailed calculations at present.A general, thermodynamic treatment of the interactions between small ligands and macromolecules is outlined. Important points are the choice of the statistical-me- chanical ensemble and considerations of the fluctuations about the mean bonding, if (i) there are not only a ligand-locus interaction but also interligand interactions (in par- ticular intdigand attraction), or (ii) there is a conformational change in themacromole- cule depending on the ligand binding. In these cases, the binding isotherms obtained from thermodynamically closed systems (canonical ensemble) may erroneously indicate a distribution about a single probability maximum, i.e., the statistical mean binding N̄, and fluctuations about this value. The description of a phase change in a bound phase or a change in the “internal” self-interactions of a macromolecule requires a bind- ing equation permitting distributions about two maxima, i.e., (i) N1* 〈 N̄ (“thin” phase) and N2* 〉 N̄ (“condensed” phase) or (ii) two macromolecular conformations P′, and P″, having occupancy numbers N̄, and N̄2, respectively. The N-F transition is an example illustrating the relation between the complete distribution functions and the two-state approximation.
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  • 48
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    Biopolymers 11 (1972), S. 493-507 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three samples of poly-γ-benzyl-L-glutamate have been prepared from γ-benzyl-N-carboxy-L-glutamate anhydride with n-hexylamine initiation at anhydride-to-initiator molar ratios, [A]/[I], of 3, 4, and 8, and their conformation and association in ethylene dichloride and dioxane have been investigated by means of infrared spectra and vapor-pressure osmometry. Two conformations, σ-and β-forms, are present in those solvents, and the content of β-form increases with increasing A/I value and concentration. At infinite dilution molecular association is absent, but the number-average molecular weight increases with cocentration, markedly in ethylene dichloride and, to a lesser extent, in dioxane. The fraction of residues involved in associated molecules have been estimated as a function of concentration. Combination of the content of β-structure with the fraction of association leads to the following results. The A/I 3 and 4 polymers form intermolecularly hydrogen-bonded aggregates, in which hydrogen-bonded residues are in the β-structure. The A/I 8 polymer has the intramolecularly hydrogen-bonded β-structure at very low concentrations, but it also forms intermolecularly hydrogen-bonded aggregates at high concentrations.
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  • 49
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    Biopolymers 11 (1972), S. 527-528 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 50
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    Biopolymers 11 (1972), S. 587-605 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dielectric studies have been carried out for the helix-coil transition of poly-β-benzyl-L-aspartate with m-cresol as a solvent. The transition of the solute molecules has been sharply reflected as a characteristic change in the dielectric dispersion curves in changing temperature. Two polarizations, one having a low and the other a high critical frequency, have appeared. According to theoretical considerations of a model of a broken helix, the former is found to come from the orientation. of helical sequences and the latter from the chemical relaxation due to the helix-coil transition. It also seems likely that the unfolded chain may have a polarizability which could not be neglected at the high-temperature side of the transition.
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  • 51
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular Dichroism measurements have been carried out on poly-L-lysine (PLL) and on random copolymers of lysine and phenylalanine at various pH values and in the presence of different amounts of NaClO4. The results indicate that either the homopolymer or the copolymers at pH conditions at which the side-chain amino groups are fully protonated, assume the right-handed α-helical conformation in the presence of NaClO4. The results are interpreted in terms of specific binding of ClO4- ions on charged side-chain amino groups.
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  • 52
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    Biopolymers 11 (1972), S. 667-678 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal denaturation of DNA's and the corresponding helix-coil transformation of artificial polyribonucleic and polydeoxyribonucleic acids have been studied extensively both theoretically1-13 and experimentally. 14-30 Much less work has been carried out on the properties of these polynucleic acids at high pressure, and in particular, on the presure dependence of the helix-coil transition temperature.31-33 Light-scattering techniques have been used in this study to measure the pressure dependence of the helix-coil transition temperature of the two- and three-stranded helices of polyriboadenylic and polyribouridilic acids and of calf thymus DNA. From the slopes of the transition temperature vs. pressure curves and heats of transition obtained from the literature,20,34 the following volume changes from these helix-coil transitions have been obtained: (a) -0.96 cc/mole of nucleotide base pairs for the poly (A + U) transition, (b) +0.35 cc/mole of nucleotide base trios for the poly (A + 2U) transition, and (c) +2.7 cc/mole of nucleotide base pairs for the DNA transition. The relative magnitudes and signs of these volume changes which show that poly (A + U) is destabilized by increased pressure, whereas poly (A + 2U) and calf thymus DNA are stabilized by increased pressure, indicates that further development of the helix-coil transition theory for polynucleotides is needed.
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  • 53
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    Biopolymers 11 (1972), S. 735-735 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 54
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    Biopolymers 11 (1972), S. 745-759 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Helix-coil transition curves are calculated for poly (dA) poly(dT) and poly (dA-dT) poly (dA-dT) using the integral equation approach of Goel and Montroll.5 The transitions are described by the loop entropy model with the exponent of the loop entropy factor, k, remaining an arbitrary constant. The theoretical calculations are compared with experimental transition curves of the two polymers. Results indicate that the stacking energies for these two polymers differ by about 1 kcal/mole of base pairs. Also, a fit between theory and experiment was not possible for k 〉 1.70.
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  • 55
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism spectra of many natural DNAs and double-stranded synthetic polynucleotides were obtained. The eight first-neighbor contributions to the CD spectra of a DNA have been extracted from these data. Therefore, the CD spectrum for any DNA with known first-neighbor frequencies may be easily calculated. For a natural DNA the CD spectrum may be approximated by assuming the first-neighbor frequencies have the most probable values consistent with the base composition. Under favorable conditions, the measured CD spectrum can be used to determine thirteen of the sixteen first-neighbor frequencies of a DNA to ± 0.02 mole percent. The TG, CA, and TA first-neighbor cannot be unambiguously resolved by our method. The accuracy of the first-neighbor frequency analysis depends on the number of different first-neighbors present in the DNA and the extent to which they differ from the most probable value.The extinction coefficient at 260 nm and the base composition can also be calculated from the CD spectrum.
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  • 56
    ISSN: 0009-2851
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  • 57
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    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 58
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    Chemie in unserer Zeit 6 (1972), S. 154-161 
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    Keywords: Chemistry ; Chemistry
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    Topics: Chemistry and Pharmacology
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  • 59
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    Chemie in unserer Zeit 6 (1972), S. 162-163 
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    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 60
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    Chemie in unserer Zeit 6 (1972), S. 164-164 
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  • 61
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    Chemie in unserer Zeit 6 (1972), S. 167-174 
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    Keywords: Chemistry ; Chemistry
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    Topics: Chemistry and Pharmacology
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  • 62
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    Chemie in unserer Zeit 6 (1972), S. 197-198 
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    Keywords: Chemistry ; Chemistry
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    Topics: Chemistry and Pharmacology
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  • 63
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    Chemie in unserer Zeit 6 (1972), S. 69-73 
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    Keywords: Chemistry ; Chemistry
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    Topics: Chemistry and Pharmacology
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  • 64
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    Chemie in unserer Zeit 6 (1972), S. 113-121 
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    Keywords: Chemistry ; Chemistry
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    Topics: Chemistry and Pharmacology
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  • 65
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    Chemie in unserer Zeit 6 (1972), S. 128-131 
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    Topics: Chemistry and Pharmacology
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    Chemie in unserer Zeit 6 (1972), S. 31-31 
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  • 67
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  • 68
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    Chemie in unserer Zeit 6 (1972), S. 32-32 
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  • 69
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  • 70
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  • 71
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    Chemie in unserer Zeit 6 (1972), S. 94-98 
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    Chemie in unserer Zeit 6 (1972), S. 99-100 
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  • 73
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    Chemie in unserer Zeit 6 (1972), S. 101-111 
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    Topics: Chemistry and Pharmacology
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  • 74
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    Chemie in unserer Zeit 6 (1972), S. 122-127 
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 7 Ill.
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  • 75
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    Chemie in unserer Zeit 6 (1972), S. 132-132 
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  • 76
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    Chemie in unserer Zeit 6 (1972), S. 164-164 
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  • 77
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    Chemie in unserer Zeit 6 (1972), S. 175-183 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 13 Ill.
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  • 78
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energies are calculated for pairs of successive bond rotations within an internal residue of a polyribonucleotide chain. Contributions to these energies include bond torsional strain, van der Waals repulsions, London attractions, electrostatic interactions, and inductive interactions between nonbonded atoms in the nucleotide repeat unit. The average dimensions of unperturbed random-coil polyribonucleotide chains are then evaluated on the basis of energies thus estimated, using for this purpose the previously developed virtual bond treatment. The characteristic ratio \documentclass{article}\pagestyle{empty}\begin{document}$ C_\infty = \mathop {{\rm lim}}\limits_{n \to \infty } (\langle r^2 \rangle_0/nl^2) $\end{document} of the mean-square end-to-end distance calculated for polyribonucleotide chains in which all pentose rings are fixed in a C3′-endo conformation is ≈9; for chains consisting exclusively of C2′-endo units it is ≈25. These values are considerably greater than those obtained by giving equal weight to all conformations judged to be sterically allowed. Satisfactory agreement between the calculations here and experimental values from viscosity and light-scattering studies is achieved by treating the chain as a random copolymer of C3′-endo and C2′-endo conformational isomers. The critical dependence of the characteristic ratio on the rotation about bond C3′-O3′ in the C2′-endo chain, however, obscures the interpretation of chain dimensions. The chain is also treated in higher approximation as a sequence of independent repeat units, each of which consists of six chemical bonds. The characteristic ratio obtained in this manner is 6.5 for the C3′-endo chain and 18.5 for the C2′-endo chain. Finally, the effects of partially stacked conformations in polyribonucleotides are investigated using the virtual bond treatment. Chain dimensions are calculated for random coil poly rA chains in which stacking is introduced by both noncooperative and cooperative processes.
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  • 79
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    Biopolymers 11 (1972), S. 315-318 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 80
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    Biopolymers 11 (1972), S. 291-301 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optial rotatory dispersion (ORD) and Circular dichroism (CD) spectra of several β-1,4 xylan and cellulose acetates and some of their oligomers were investigated. The CD spectra proved considerably superior in terms of information content and interpretability. Comparison of the xylan and cellulose acetate series which also included partially substited cellulose acetates showed that the sign of the CD of the C(6) acetyl was negative. Likewise, the combined contribution of C(1) and C(4) to their equatorially substituted acetyls was positive (with C(1) definitely Positive) and the combined contribution of C(2)eq and C(3)eq negative. The solution conformations of both polysaccharide acetates appeared to be random. The CD of White birch xylan acetate which is substituted on the average at every tenth residue with a 4-O-methyl glucuronic acid substituent, was sensitive to it. The xylan oligomer series also illustrated that CD may be used to determine the degree of polymerization of these oligomers up to about 20.
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  • 81
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mean square of dipole moment of a linear macromolecule which is responsible for dielectric increment of aqueous polyelectrolyte solutions is calculated by means of a matrix method in which ion binding at discrete sites and the nearest-neighbor interaction are taken into account. On the basis of the relationship between polarization of poly-ion and fluctuation of bound counterions the present theory indicates that the loosely bound ions result in larger increment and otherwise smaller increment. Also, the theory predicts that the dielectric increment has a maximum at an intermediate monovalent-divalent ion ratio when both species coexist. These results are consistent with experiments on polyacrylic acid neutralized with NaOH and Ca(OH)2. At large contents of divalent ions the effect of chelation is also discussed.
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  • 82
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    Biopolymers 11 (1972), S. 399-408 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 220-MHz NMR spectra of various poly (N-alkylamino acid)s are investigated. Spectra of polysarcosine recorded in various solvents showed fine splittings of the methyl and methylene bands. Comparing the spectrum with that of its model compound, the fine structure of the methyl band of polysarcosine was assigned to four dyad sequences of the cis-trans isomeric state of the main chain amide bonds. Also the methylene band was roughly divided into cis and trans bands. From the temperature dependence of the spectra of polysarcosine, a double coalescence phenomenon was observed, in which the four dyad peaks coalesced into two peaks corresponding to cis and trans, then the two peaks coalesced into one peak. Further, the approximate value of the free energy for the internal rotation of the main chain amide bond was estimated. NMR spectra of various poly(N-alkylglycine)s in methylene chloride solution were also obtained. From the comparsion of their methylene bands, the introduction of the bulky N-alkyl groups was found to increase the cis content of the amide bond.
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  • 83
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    Biopolymers 11 (1972), S. 443-459 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When exposed to a low pH, in various ionic strength conditions and in sufficiently dilute solutions, DNA undergoes a transition, revealed by an increase in optical density. A careful analysis shows that, associated with this transition, there is an effective decrease in absorbance, overcompensated by an increase in scattering. The conditions for the new transition can be summarized conveniently by a graph in a pH-Na+ molarity diagram. If the pH of a DNA solution is progressively lowered at constant Na+ concentration, one finds first the melting transition (I), and at lower pH values, the new transition (II). If the same experiment is performed on pre-denatured DNA, only transition II will be found. If native DNA is brought directly to the low pH conditions, without allowing it to denature irreversibly at intermediate pH values, transition II is reversible (with a small hysteresis effect). DNA, initially native, neutralized after prolonged exposures to the low pH, recovers the buoyant density value of native DNA, along with the absorption and scattering properties of the native state. The experiments are consistent with the interpretation that a new state exists in which DNA, still double stranded, assumes a very compact shape (of the order of 1500 Å in diameter for T2 DNA), with a hyperchromicity value of 10-14% above the native value. Nearly monodisperse suspensions of DNA molecule in this apparent state may be obtained only at very low concentrations (∼0.25 μg/ml). At 1 μg DNA/ml aggregation is noticeable. The possible connection with the condition of intraphage DNA is discussed.
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  • 84
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyethyleneimine and its acyl derivatives have been thiolated with thiobutyrolactone and the SH groups introduced have been crosslinked in the presence of and in the absence of methyl orange, respectively. After crosslinking of the polymers, the bound methyl orange was removed. The resultant two kinds of crosslinked polymers have been examined for their ability to bind methyl orange. The polymer crosslinked in the presence of methyl orange shows more binding sites and stronger binding than does the polymer crosslinked in the absence of methyl orange. It seems, therefore, that the conformation of the polymer may be molded to provide sites that can accommodate a specific small molecule.
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  • 85
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    Biopolymers 11 (1972) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 86
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    Biopolymers 11 (1972), S. 563-586 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 87
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electro-optic measurements are reported for the polynucleotides poly A, poly U, poly G, and NaDNA, and their complexes with acridine orange (AO). Measurements were also made on the methylene blue (MB) complex with NaDNA. Poly U, poly G, and NaDNA complexes with AO as well as the NaDNA-MB complex were found to exhibit positive birefringence and perpendicular dichroism indicating the dye molecules are oriented with their long axes perpendicular to the applied electric field. The opposite was found for the AO complex with poly A, which showed positive birefringence and parallel dichroism, indicating that in this case the dye molecules are oriented with their long axes parallel to the field.
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  • 88
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    Biopolymers 11 (1972), S. 679-682 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radius of gyration and “persistence length” of poly-L-alanine, calculated from small-angle x-ray scattering data, have values of 56 Å and 44 Å, respectively, in dichloroacetic acid, and 78 Å and ∼30 Å in a 1:1 v/v mixture of trifluoroacetic acid and trifluoroethanol. This can be interpreted to mean that poly-L-alanine exists in a relatively rigid, predominantly α-helical conformation in dichloroacetic acid and in an extended, more flexible form in the mixed solvent system.
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  • 89
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    Biopolymers 11 (1972), S. 761-779 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature dependence of the circular dichroism and ultraviolet absorbance of calf thymus DNA and poly dAT were measured in aqueous solutions of various 1-1 electrolytes. Although there was very little change in absorbance, the circular dichroism changed dramatically as a function of both temperature and solvent. There is a correlation of the heat of hydration of the cation and the magnitude of the temperature dependence of the circular dichroism. Our results are interpreted in terms of a large number (possibly a continuum) of intermediate secondary structures.
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  • 90
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    Biopolymers 11 (1972), S. 849-852 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 91
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    Biopolymers 11 (1972), S. 881-892 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The study of anisotropy light scattering from tapioca and potato starches has continued with the recording of more detailed experimental single-granule Hv scattering patterns and, for the first time, single-granule Vv patterns. Quantitative analysis of the higher order scattering maxima to the granule morphology, permitting an analysis of the latter in terms of a lyered structure. For tapioca starch, this analysis indicates that if layering is present at all, the layer thickness is comparable to the wavelength of the incident radiation, and most likely is considerably less than 0.5 μ in thickness. On the other hand, the potato starch morphology is characterized by a relatively coarse layering with few layers and considerable difference in the anisotropy between successive layers. The models for the two starches in best agreement with experimental data are as follows: almost perfectly spherulitic anisotropic structure with very thin shell-like layers - if any - for tapioca, and alternating layers of varying anisotropy several microns in thickness and probably simultaneously present with an isotropic center, for potato starch. The Vv pattern for tapioca starch is in agreement with this model, although its information content is lower owing to the experimental difficulty of recording higher order maxima. Suggestions for further morphological study of starches are presented.
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  • 92
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    Biopolymers 11 (1972), S. 951-955 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The techniques of the previous article are here applied to the case for which the solution contains, in addition to excess uni-univalent salt, one equivalent of divalent counterions per mole nucleotide. In agreement with the melting temperature measurements of Dove and Davidson for Mg++, it is predicted that a region of uni-univalent salt concentration then exists in which (dT m/d log m A+) is negative. It is further predicted, in accord with experiment, that in the presence of divalent counterions, the helical form of DNA is much more stable than in their absence.
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  • 93
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    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 1021-1030 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The theoretical change of the mean-square dipole moment of a polypeptide during the helix-coil transition is compared with the change in helix content. It is shown that, according to the theory, the determination of the helix initiation parameter σ and the enthalpy of helix formation ΔH can be determined. Experimental data on poly-benzyl-L-gluatamate in two different solvent mixtures are given.
    Additional Material: 3 Ill.
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  • 94
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    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 1031-1039 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ultraviolet absorption, optical rotatory dispersion, circular dichroism, and infrared absorption spectra of renatured 5S RNA have been measured at pH 7.0 in 0.1M NaCl at 25° and used to obtain four independent estimates of the number of base pairs. These four estimations are in reaonable agreement and average values of 28 ± 4 G.C and 13 ± 4 A.U. base pairs.
    Additional Material: 4 Ill.
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  • 95
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 1116-1116 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 96
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 1137-1148 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Far-infrared spectra in the region from 700 to 200 cm-1 were measured for the copolymers of L-alanine and glycine, those of L-alanine and L-valine, those of L-alanine and L-leucine, and those of L-alanine and L-phenylalanine. The observed spectra were interpreted on the basis of the analysis of the far-infrared spectra of the corresponding homopolymers, and the correlation between the conformations of the copolymers and the kinds of the component amino acids was discussed.
    Additional Material: 8 Ill.
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  • 97
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    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 1149-1171 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have calculated rotational strengths and circular dichroism (CD) curves for sidechain and backbone transitions in poly-L-Phenylalanine (PLP), POLY-p-amino-L-phenylalanine (PPALP), poly-p-chloro-L-phenylalanine (PPCLP), poly-o-acetyl-L-tyrosine (POALT), and poly-p-nitro-L-phenylanine (PPNLP), using methods applied previously to poly-L-tyrosine (PLT). Comparison of the theoretical CD curves with available experimental data for PLP and PPALP indicate that these polypeptides form right-handed helices with side-chain conformations similar to that of PLT. For PPNLP, where experimental data are also available, no conformational assignment could be made, as none of the calculated curves gave good agreement with experiment. Possible reasons for this lack of agreement are discussed. For the other two polypeptides, PPCLP and POALT, although no experimental data are yet available, the calculated curves indicate that an unambiguous assignment should be possible. For the conformations (RA and LA) in which the side chains are packed more loosely, there are strong similarities in the calculated CD curves of a particular conformation, regardless of the para substituent. In the tighter R1 and L1 conformations, few generalizations can be drawn, each derivative having a distinctive pattern. In PLP, PPCLP, and POALT, where the side-chain La band is in the 200-210 nm region, the L1 conformation exhibits a negative nπ* rotational strength, opposite to that expected for a left-handed helix. One must therefore be cautious about assigning the helix sense of aromatic polypeptides on the basis of the sign of the nπ* CD band. Side-chain nπ* transitions present in POALT and PPNLP were found to have small rotational strength.
    Additional Material: 13 Ill.
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  • 98
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the effect of linkage on the possible conformations of di-and polysaccharides of α-D-glucose and also the probable intramolecular hydrogen bonds has been made. The differences in the nature of linkage is shown to effect the energetically preferred conformations; (1 → 2) linkages lead only to righthanded helical conformations, (1 → 3) linkages lead to extended as well as both left and righthanded helical conformations; (1 → 4) linkages lead to both right-and lefthanded wide helical conformations. The possible hydrogen bonds between adjacent residues are also dependent on the nature of the linkage. A comparison of the conformational data of α-D-glucans with those of β-D-glucans has indicated that the favored conformations and hydrogen bonds between contiguous residues in the chain are influenced by the configuration at the anomeric carbon atom in all the three types of polysaccharides. From the energy calculations a probable conformation (φM = -10°, ψM = -30°, φN = -23°, ψN = -19°) has also been proposed for crystalline mycodextran in conformity with x-ray data. This conformation contains two types of hydrogen bonds between contiguous residues one between 0-2 and 0-3 atoms at (1 → 4) linkage and the other between 0-2 and 0-4 atoms at (1 → 3) linkage in the chain. The conformation of maltose unit (-10°,-30°) that is likely to occur in the crystalline mycodextran coincides with the minimum energy conformation of maltose.
    Additional Material: 11 Ill.
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  • 99
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 1395-1410 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction between poly C and (Gp)nG(n = 1,2) in dilute solution was investigated spectrophotometrically in 0.1M phosphate buffer pH 7.2 under conditions unfavorable for the formation of self-associated complexes of oligoguanylic acids. Two isosbestic points were observed when poly C was titrated gradually with GpGpG, one at 232-233 mμ(in the range of 0-33% poly C) and one around 238 mμ (in the range of 50-100% poly C). The melting temperature (Tm) of the 1:1 poly C: (Gp)nG complexes (n = 1,2) of varying concentration were determined. The equilibrium properties of the 1:1 complexes can be described by two interaction parameters, namely, (i) cooperative stacking interaction between the first nearest neighbor of the adsorbed oligomer, and (ii) intrinsic association constant of the adsorbed oligomer with its polymeric site, since the cooperative helix-coil transition particularly in the smaller oligonucleotide can be described by an “all or none” model. Based on such a model the enthalpy of stacking inteaction-dependent Tm values yielded directly the sum of the enthalpy of stacking interaction and of basepairing (which is dependent on the chain length of the oligomer) and the value of S, the stability constant of a G-C pair within a helix. The enthalpy of formation of G-C pair is then calculated as -6.3 kcal/base pair either from the chain length dependent enthalpy term or from the temperature coefficient of S values. From the S value and the association constant of 1:1 GpGpGpC:GpCpCpC complex, other thermodynamic parameters such as nucleation parameter (β) and free energy of stacking interaction can be obtained.
    Additional Material: 6 Ill.
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  • 100
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 1317-1333 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Equilibrium dialysis and electronic and nuclear resonance spectroscopy show that tRNA cooperatively binds divalent metal ions at very low concentrations (free metal concentration 3 × 10 -6 M). The first two methods show that different purified tRNAs have a very similar behavior, including initiator tRNAFmet. tRNAs with an extra arm in the clover-leaf model, however, appear to have a slightly different behavior.The binding can be described in terms of two classes of sites. The cooperative association of divalent ions binding first does not parallel a cooperative change in the hyperchromism of the tRNA, while the non-cooperative association of the second class of divalent ions corresponds to the concentrations needed to obtain a cooperative melting of the tRNA.The temperature dependence of the number of binding sites and of their binding constants is also presented.The nature of the divalent ion gives the following efficiency: for the cooperativity Co++〉Mg++〉Mn++ for the weak binding sites Mn++〉Co++〉Mg++
    Additional Material: 8 Ill.
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