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  • Pyrophosphate
  • Springer  (28)
  • MDPI Publishing
  • 1
    ISSN: 1433-4909
    Keywords: Key words Phosphofructokinase ; Pyrophosphate ; Dictyoglomus thermophilum ; Polyphosphate ; Tripolyphosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The distribution of phosphofructokinase phosphoryl donor subtypes (ATP-, ADP-, and pyrophosphate) in the deeply rooted phylogenetic lineages of thermophiles is of interest with regard to the evolution of phosphofructokinase activity and of the Embden–Meyerhof pathway. In this article we present the first biochemical description of a thermostable pyrophosphate-dependent phosphofructokinase from the hyperthermophilic bacterium Dictyoglomus thermophilum. The enzyme was not allosterically controlled by traditional modulators of phosphofructokinases and has significant activity with tripolyphosphate and polyphosphate. Kinetic parameters of the enzyme suggest it plays primarily a glycolytic role. The enzyme required Mg2+ for optimal activity, was partially activated by some monovalent and divalent cations, and was strongly inhibited by Cu2+. The sequence of the 21 N-terminal residues sug-gests that the enzyme is most similar to the pyrophosphate-dependent phosphofructokinases from Amycolatopsis methanolica and the hyperthermophilic crenarchaeon Thermoproteus tenax, enzymes which have been suggested to represent an ancient lineage of phosphofructoki-nases (Siebers et al. 1998). The unexpected finding of a pyrophosphate-dependent phosphofructokinase in Dictyoglomus thermophilum, which is phylogenetically related to Thermotoga maritima, previously shown to possess an ATP-dependent phosphofructokinase activity, is discussed.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 20 (1995), S. 77-82 
    ISSN: 1432-0789
    Keywords: Soil enzymes ; β-Glucosidase ; Humic/enzyme complexes ; Enzymatic extration ; Pyrophosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Humic compounds with β-glucosidase activity were extracted from soil using tetrasodium pyrophosphate as extracting solution. Mixture of soil samples with 0.01 M pyrophosphate in a ratio of 1:5 (w/v), adjustment to pH 7.0–7.3, extraction for 18 h with reciprocating agitation, and bacteriological filtration after centrifugation were the optimum conditions for extraction of the β-glucosidase complexes. Otherwise, experimental conditions for extraction indicated that the concentration and pH of pyrophosphate were the factors with the most influence on enzymatic extraction yields. The results indicated that the β-glucosidase was extracellular and associated with soil humates.
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  • 3
    ISSN: 1432-2048
    Keywords: Glycolysis ; Phloem ; Pyrophosphate ; Ricinus ; Sucrose synthase ; Transport
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Metabolites and enzyme activities were measured in the phloem sap exuding from a cut hypocotyl of germinating castor-bean (Ricinus communis L.) seedlings. The sap contained considerable quantities of adenine nucleotides, uridine nucleotides, uridine diphosphoglucose (UDPGlc), all the major phosphorylated metabolites required for glycolysis, fructose-2,6-bisphosphate and pyrophosphate. Supplying 200 mM glucose instead of sucrose to the cotyledons resulted in high concentrations of glucose in the sap, but did not modify the metabolite levels. In contrast, when 200 mM fructose was supplied we found only a low level of fructose but a raised sucrose concentration in the sap, which was accompanied by a three-to fourfold decrease of UDPGlc, and an increase of pyrophosphate, UDP and UTP. The measured levels of metabolites are used to estimate the molar mass action ratios and in-vivo free-energy change associated with the various reactions of sucrose breakdown and glycolysis in the phloem. It is concluded that the reactions catalysed by ATP-dependent phosphofructokinase and pyruvate kinase are removed from equilibrium in the phloem, whereas the reactions catalysed by sucrose synthase, UDPGlc-pyrophosphorylase, phosphoglucose mutase, phosphoglucose isomerase, aldolase, triose-phosphate isomerase, phosphoglycerate mutase and enolase are close to equilibrium within the conducting elements of the phloem. Since the exuded sap contained negligible or undetectable activities of the enzymes, it is concluded, that the responsible proteins are bound, or sequesterd behind plasmodesmata, possibly in the companion cells. It is argued that sucrose mobilisation via a reversible reaction catalysed by sucrose synthase is particularily well suited to allow the rate of sucrose breakdown in the phloem to respond to changes in the metabolic requirement for ATP, and for UDPGlc during callose production. It is also calculated that the transport of nucleotides in the phloem sap implies that there must be a very considerable uptake or de-novo biosynthesis of these cofactors in the phloem.
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  • 4
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    Monatshefte für Chemie 124 (1993), S. 381-389 
    ISSN: 1434-4475
    Keywords: Co2(P2O7)·2H2O ; Co2(As2O7)·2H2O ; Pyrophosphate ; Pyroarsenate ; Co(II)O6 octahedron
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Kristalle von Co2(X 2O7)·2H2O,X=P/As wurden unter Hydrothermalbedingungen synthetisiert. Ihre Kristallstrukturen wurden mittels Röntgenbeugung an Einkristallen bestimmt:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2) Å, β=94.77(2)/97.74(2)°, Raumgruppe P21/n,R=0.032/0.046,R w=0.028/0.034 für 2423/2042 Reflexe und 131/119 Variable. In den beiden über eine gemeinsame Ecke zuX 2O7-Gruppen verknüpftenXO4-Tetraedern sind die mittleren 〈P-O〉-Abstände ungefähr gleich (1.540 und 1.543 Å), hingegen differiert 〈As-O〉 signifikant (1.685 und 1.696 Å). Ein Vergleich mit den isotypen Mn- und Mg-Pyrophosphaten zeigt eine Korrelation zwischen dem Quotienten 〈Me-O〉/〈X-O〉 und dem WinkelX-O-X.
    Notes: Summary Crystals of Co2(X 2O7)·2H2O,X=P/As were synthesized under hydrothermal conditions. Their crystal structures were determined by single crystal X-ray diffraction:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2)Å, β=94.77(2)/94.74(2)°, space group P21/n,R=0.032/0.046,R w=0.028/0.034 for 2423/2042 reflections and 131/119 variables. Within the twoXO4 tetrahedra connected via a common corner to anX 2O7 group the average 〈P-O〉 bond lengths are approximately equal (1.540 and 1.543 Å), but 〈As-O〉 differs significantly (1.685 and 1.696 Å). A comparison with the isotypic Mn and Mg pyrophosphates shows a correlation between the ratio 〈Me-O〉/〈X-O〉 and the angle O-X-O.
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  • 5
    ISSN: 1432-1432
    Keywords: Transphosphorylation ; Pyrophosphate ; Precipitated magnesium phosphate ; Phospho(enol)pyruvate ; Phosphorolysis ; Chemical evolution ; Inorganic enzyme
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The enzyme-like kinetic properties of precipitated magnesium phosphate as a catalyst for formation of pyrophosphate (PPi) from phospho (enol)pyruvate (PEP) are described. This synthesis occurs at a low temperature (37°C) and represents a model that may help us understand the relevance to chemical evolution of minerals as ancient catalysts whose functions could have been taken over by contemporary enzymes. An insoluble Pi.Mg matrix was formed in a medium with 80% of the water replaced by dimethyl sulfoxide as a way of simulating conditions in a drying pond. Phospho(enol)pyruvate adsorbs onto the Pi.Mg surface according to a Langmuir isotherm, and the PEP concentration dependence of PPi formation follows a Michaelian-like function. A yield of 33% for transformation of the initially adsorbed PEP into PPi was attained after 4 days of incubation with equimolecular concentrations of Pi, MgCl2, and PEP. The magnesium concentration dependence for Pi and Mg precipitation, for adsorption of PEP onto solid Pi.Mg, and for PPi formation showed complex cooperative behavior. These results taken as a whole lead to the conclusion that the Pi.Mg surface not only provides a reactant for PPi formation but also catalyzes the reaction.
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  • 6
    ISSN: 1432-2048
    Keywords: Carbohydrate turnover ; Cell culture (triose phosphate recycling) ; Chenopodium ; Pyrophosphate ; fructose-6-phosphate phosphotransferase ; Triose phosphate cycling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Experiments were carried out to determine whether pyrophosphate: fructose-6-phosphate phosphotransferase (PFP) catalyses the rapid recycling of triose phosphates that is found in the cytosol of heterotrophic cell cultures of Chenopodium rubrum L. (W.-D. Hatzfeld, M. Stitt, 1990, Planta, 180, 198–204). Oxygen uptake, carbohydrate turnover, fructose 2,6-bisphosphate (Fru2,6bisP), glycolytic intermediates, adenine and uridine nucleotides, pyrophosphate and the activity of PFP and glycolytic enzymes were monitored for 48 h after subculturing carbohydrate-depleted cells onto glucose. Immediately after transfer there was an increase in the amount of Fru2,6bisP, and of the hexose phosphate. The triose phosphates, fructose-1,6-bisphosphate and inorganic pyrophosphate increased gradually over the next 24 h. This was accompanied by a tripling in the extractable activity of PFP, but not of phosphofructokinase. The activity of fructose-1,6-bisphosphatase was 20–50fold lower than that of PFP. It is calculated that the activity of PFP is high enough to catalyse the observed rate of cycling between the triose phosphates and the hexose phosphates, based on the measured Vmax capacity of the enzyme, the known kinetic properties, and the measured levels of its reactants and Fru2,6bisP. The changes in the levels of Fru2,6bisP were not correlated with the rate of respiration. Instead, the rate of O2 uptake was inversely related to the phosphoenolpyruvate level, showing that pyruvate kinase or phosphoenolpyruvate carboxylase are regulating the use of glucose for respiration. There was also no relation between Fru2,6bisP, and partitioning to sucrose or starch. It is proposed that the main function of the cycle in these cells is to maintain high levels of inorganic pyrophosphate and triose phosphates, which are necessary for the remobilisation of sucrose and for biosynthesis in the plastid, and that ‘coarse’ and ‘fine’ control of PFP play an important role in regulating this cycle.
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  • 7
    ISSN: 1432-072X
    Keywords: Anaeroplasma ; Asteroleplasma ; Glycolysis ; Mollicutes ; PPi-phosphofructokinase ; Purines ; Pyrimidines ; Pyrophosphate ; Carbohydrate metabolism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Cell-free extracts of two strictly anaerobic mollicutes, Anaeroplasma intermedium 5LA and Asteroleplasma anaerobium 161T, were tested for enzymic activities of intracellular carbohydrate metabolism. Asteroleplasma anaerobium was also tested for enzymes of purine and pyrimidine metabolism. Both organisms had enzymic activities associated with the nonoxidative portion of the pentose phosphate pathway, and with the Embden-Meyerhoff-Parnas pathway. The 6-phosphofructokinase (PFK) of Asteroleplasma anaerobium was ATP-dependent, whereas the PFK of Anaeroplasma intermedium was PPi-dependent. The two anaerobic mollicutes also differed with respect to the enzymes that converted phosphoenolpyruvate (PEP) to pyruvate; Anaeroplasma intermedium had pyruvate kinase activity, but Asteroleplasma anaerobium had pyruvate, orthophosphate dikinase activity (PPi-dependent). Both organisms had lactate dehydrogenase activity which was activated by fructose 1,6-bisphosphate (Fru-1,6-P 2). Anaeroplasma intermedium had activity for PEP carboxykinase (activated by Fru-1,6-P 2), but Asteroleplasma anaerobium did not. PEP carboxytransphosphorylase activity was not detected in either organism. Anaeroplasma intermedium had malate dehydrogenase and isocitrate dehydrogenase activities, but it had no activities for the three other tricarboxylic acid cycle enzymes examined; Asteroleplasma anaerobium had malate dehydrogenase activity only. Asteroleplasma anaerobium had enzymic activities for the interconversion of purine nucleobases, (deoxy)ribonucleosides, and (deoxy)ribomononucleotides, including PPi-dependent nucleoside kinase, reported heretofore only in some other mollicutes. Asteroleplasma anaerobium could synthesize dTDP by the thymine salvage pathway if deoxyribose 1-phosphate was provided, and it had dUTPase, ATPase, and dCMP kinase activities. It lacked (deoxy)cytidine deaminase, dCMP deaminase, and deoxycytidine kinase activities.
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  • 8
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    Protoplasma 136 (1987), S. 205-207 
    ISSN: 1615-6102
    Keywords: ATP ; Nitella ; Proton pump ; Pyrophosphate ; Tonoplast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
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  • 9
    ISSN: 1432-072X
    Keywords: Polyphosphate ; Pyrophosphate ; ATP ; Fusidium coccineum ; Biosynthesis of antibiotic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Two strains of Fusidium coccineum showing different activities in fusidic acid formation were compared. The ATP and polyphosphate contents of the highly active strain was found to be less than those of the low activity strain. At the same time, higher levels of pyrophosphate and a lower activity of pyrophosphatase were observed in the highly active strain during intensive biosynthesis of fusidic acid as compared to those in the low activity strain. The high levels of pyrophosphate might be due not only to the low pyrophosphatase activity but also to formation of pyrophosphate from ATP used for the synthesis of fusidic acid.
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  • 10
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    Journal of molecular evolution 18 (1981), S. 24-29 
    ISSN: 1432-1432
    Keywords: Thioester ; Pyrophosphate ; Tripolyphosphate ; Phosphorylimidazole ; Molecular evolution ; Prebiotic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Reaction of 0.20M orthophosphate with 0.20M N,S-diacetylcysteamine in 0.40M imidazole at pH 7.0 or 8.0 under drying conditions at 50°C for 6 days yields pyrophosphate and tripolyphosphate in the presence and absence of 0.10M divalent metal ion. The efficiency of utilization of N,S-diacetylcysteamine in the formation of pyrophosphate linkages ranges from 3 – 8% under the above conditions. The thioester, N,S-diacetylcysteamine, and imidazole are required for phosphoanhydride formation. Reaction of 0.40M orthophosphate with 0.20M N, S-diacetylcysteamine in 0.40M imidazole at ambient temperature for 6 days yields phosphorylimidazole in the absence or presence of 0.05M MgCl2. Phosphorylimidazole and pyrophosphate are formed in the presence of 0.05M CaCl2; pyrophosphate and tripolyphosphate are formed with 0.15M CaCl2. The efficiency of utilization of N,S-diacetylcysteamine in the formation of pyrophosphate linkages is roughly 7% at 6 days of reaction with 0.15M CaCl2. The thioester, N,S-diacetylcysteamine and imidazole are required for the formation of phosphoanhydrides. The significance of these reactions to molecular evolution is discussed.
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  • 11
    ISSN: 1432-072X
    Keywords: Pyrophosphate ; Polymerie acid-soluble poly-phosphates ; Budding process ; Yeast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In the cells of hybrid yeast strain Saccharomyces N.C.Y.C. 644 SU3 (Karlsberg collection), a large amount of pyrophosphate (30–300 μmol/g of dry weight) accumulates whatever the aeration conditions and the content of glucose in the medium. The content of pyrophosphate is 10–1000 times higher than that of ATP. At the early and mid-exponential growth phases two maxima of pyrophosphate accumulation are observable. The periods of maximal pyrophosphate accumulation in yeast coincide with those of the minimal content of polymeric acid-soluble polyphosphates and intense budding. In the light of the data obtained, the question is discussed as to the relationship between the metabolism of pyrophosphates and acid-soluble polyphosphates in yeast.
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  • 12
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    Journal of molecular evolution 15 (1980), S. 161-168 
    ISSN: 1432-1432
    Keywords: Prebiotic synthesis ; Proteinoid ; Lysine-Rich ; ATP ; Pyrophosphate ; Peptides ; Cellular synthesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Lysine-rich proteinoids in aqueous solution catalyze the formation of peptides from free amino acids and ATP. This catalytic activity is not found in acidic proteinoids, even though the latter contain some basic amino acid. The pH optimum for the synthesis is about 11, but is appreciable below 8 and above 13. Temperature data indicate an optimum at 20°C or above, with little increase in rate to 60°C. Pyrophosphate can be used instead of ATP, with lesser yields resulting. The ATP-aided syntheses of peptides in aqueous solution occur with several types of proteinous amino acid.
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  • 13
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    Calcified tissue international 31 (1980), S. 147-151 
    ISSN: 1432-0827
    Keywords: Apatite ; Citrate ; Pyrophosphate ; Calcination ; “Citrate-apatite”
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary An apatite containing citrate ions has been synthesized. Measurements of specific surface, as well as Ca/P ratio, infrared, X-ray, and calcination data are all consistent with the idea that citrate ion substitutes for PO 4 3− ion on the apatitic surface.
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  • 14
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    Calcified tissue international 25 (1978), S. 19-21 
    ISSN: 1432-0827
    Keywords: Bone membrane ; Pyrophosphate ; Calvaria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary The flux of32P-labeled inorganic pyrophosphate (PPi) into bone was studied in vitro using Ussing chamber techniques and calvaria from newborn rat pups. Because insignificant hydrolysis and backflux of PPi took place under experimental conditions, it was possible to study the penetration of bone membranes by PPi unambiguously. At physiological concentrations, the influx was found to be linearly concentration dependent and to follow first order kinetics, apparently a simple diffusion process. In magnitude, the intrinsic constant for influx was found to be approximately one-half that of inorganic phosphate ions under comparable conditions.
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  • 15
    ISSN: 1432-0827
    Keywords: Dentin ; Calcification ; Pyrophosphate ; Enzyme
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Après incubation de coupes de germes de molaires de rats, fixés aux aldéhydes, dans une solution alcaline de pyrophosphate de plomb, une réaction positive de coloration au sulfure est localisée au niveau du front de minéralisation de la dentine, dans le stratum intermedium et les cellules sous-odontoblastiques. Au microscope électronique, le nombre et la taille de cristaux, en forme d'aiguilles, sont augmentés dans la zone en voie de minéralisation (denture intermédiaire). Un fin précipité est surtout observé dans les noyaux du stratum intermedium et les cellules sous-odontoblastiques. Les effects de l'EDTA, Zn2+, Ca2+, Mg2+ et citrate sont aussi étudiés et la probabilité d'activité en pyrophosphatase inorganique est discutée en fonction des dépôts de plomb observés. L'action d'une pyrophosphatase inorganique sur la précipitation du phosphate de plomb ne peut être exclue. Cependant, la réaction de coloration peut être aussi due à une absorption non catalysée de composé de plomb sur les cristaux d'apatite.
    Abstract: Zusammenfassung Schnitte von Ratten-Molarkeimen, die mit Aldehyd fixiert und in einer alkalischen Blei-Pyrophosphat-Lösung inkubiert wurden, zeigten an folgenden Stellen eine positive Sulfid-Färbungsreaktion: in der Mineralisierungsfront des Dentins, im Stratum intermedium, und in den subodontoblastischen Zellen. Elektronenmikroskopisch waren Anzahl und Größe der sichtbaren, nadelartigen Kristallite in der Mineralisationszone (intermediäres Dentin) erhöht. Ein feiner Niederschlag konnte vorwiegend in den Nuclei des Stratum intermedium und der subodontoblastischen Zellen beobachtet werden. Es wurde zudem die Wirkungsweise von EDTA, Zn2+, Ca2+, Mg2+ und Zitrat untersucht. Schließlich wird die Wahrscheinlichkeit einer Aktivität von anorganischer Pyrophosphatase im Zusammenhang mit den beobachteten Bleiablagerungen besprochen. Daß anorganische Pyrophosphatase bei der Fällung von Bleiphosphat eine Rolle Spielt, ist nicht auszuschließen. Allerdings kann die Farbreaktion auch durch nicht-katalysierte Adsorption der Bleiverbinding an die Apatitkristalle bedingt sein.
    Notes: Abstract After incubation of aldehyde-fixed sections of rat molar germs in an alkaline solution of lead pyrophosphate, a positive sulphide staining reaction was observed in the mineralization front of the dentin, in the stratum intermedium, and in the subodontoblastic cells. In the electron microscope, the number and size of visible needle-like crystallites was increased in the mineralization zone (intermediate dentin). A fine precipitate was observed predominantly in the nuclei of the stratum intermedium and subodontoblastic cells. The effects of EDTA, Zn2+, Ca2+, Mg2+ and citrate were also studied and the probability of inorganic pyrophosphatase activities is discussed in relation to the observed lead deposits. The interaction of an inorganic pyrophosphatase cannot be excluded in the precipitation of lead phosphate. However, the staining reaction may also be due to uncatalyzed adsorption of the lead compound onto the apatite crystals.
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  • 16
    ISSN: 1432-0827
    Keywords: Acid phosphate ; Apatite ; Carbonate ; Pyrophosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Le rapport molaire Ca/P, % CO 3 2− et % HPO 4 2− sont déterminés pour un certain nombre d'apatites préparés par hydrolyse de phosphate de calcium amorphe en présence de solution de carbonate. Le rapport molaire Ca/P pour chaque apatite est significativement plus élevé que celui du précurseur amorphe correspondant. Le changement en contenu de carbonate est faible, mais la concentration en HPO 4 2− de ces apatites, déterminée selon la technique pyrolytique habituelle, est nettement réduite, et atteint souvent une valeur nulle. L'analyse infra-rouge montre, d'autre part, une concentration appréciable de HPO 4 2− . Il semble que le carbonate réagit au cours de la pyrolyse avec HPO 4 2− soit en bloquant une condensation de P2O 7 4− ou en dégradant du P2O 7 4− déjà formé. Il apparait qu'il faut utiliser la méthode de pyrolyse avec prudence pour déterminer la présence de HPO 4 2− dans les tissus calcifiés.
    Abstract: Zusammenfassung Das molare Ca/P-Verhältnis sowie die prozentualen Anteile von CO 3 2− und HPO 4 2− wurden bei einer Anzahl von Apatiten bestimmt, welche durch Hydrolyse von amorphem Calciumphosphat, bei Anwesenheit von Karbonat in der Lösung, erhalten wurden. Das molare Ca/P-Verhältnis war bei jedem Apatit bedeutend höher als bei der entsprechenden amorphen Vorstufe. Das Karbonat veränderte sich wenig, jedoch war der HPO 4 2− -Gehalt dieser Apatite, mittels der pyrolytischen Standard-Technik bestimmt, stark reduziert und lag manchmal nahe beim Nullwert. Andererseits zeigte die Infrarot-Analyse eindeutig einen beträchtlichen HPO 4 2− -Gehalt. Somit wird bewiesen, daß Karbonat die pyrolytische Bestimmung von HPO 4 2− stört, entweder indem es die Kondensation zu P2O 7 4− blockiert oder schon gebildetes P2O 7 4− abbaut. Es wird vorgeschlagen, daß die pyrolytische Methode zur Bestimmung von HPO 4 2− in verkalktem Gewebe nur mit großer Vorsicht anzuwenden ist.
    Notes: Abstract The Ca/P molar ratio, % CO 3 2− , and % HPO 4 2− was determined for a number of apatites prepared by the hydrolysis of amorphous calcium phosphate in the presence of solution carbonate. The Ca/P molar ratio for each apatite was significantly higher than for the corresponding amorphous precursor. The change in carbonate content was slight but the HPO 4 2− level in these apatites, as determined by the standard pyrolytic technique, was greatly reduced, sometimes to a near zero value. Infrared analysis, on the other hand, clearly showed an appreciable level of HPO 4 2− . Evidence obtained indicated that the carbonate interferes with the pyrolytic assay for HPO 4 2− by either blocking condensation to P2O 7 4− or by breaking down already formed P2O 7 4− . It is suggested that the pyrolytic method be used with great caution in assaying for HPO 4 2− in calcified tissue.
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  • 17
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    Calcified tissue international 14 (1974), S. 169-175 
    ISSN: 1432-0827
    Keywords: Galactose ; Glucose-6-phosphate ; Resorption ; Pyrophosphate ; Hydroxyproline ; Alkaline phosphatase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'effet du galactose sur le métabolisme osseux est étudié en soumettant de jeunes rats à un régime semi-synthétique contenant 35% de ce monosaccharide. Les animaux témoins reçoivent le même régime sans galactose, avec du glucose. L'effet d'une consommation de Ca−P, normal et faible, est étudié chez les témoins et les groupes soumis au galactose. La glucose-6-phosphate deshydrogénase osseuse est inhibée lorsque le galactose s'accumule dans les tissues. L'excrétion urinaire de calcium, pyrophosphate, aminopolysaccharides, hydroxyproline en phosphatase alcaline plasmatique (isoenzyme osseuse) est augmentée de façon significative par rapport aux témoins. Les animaux, recevant du galactose avec un régime faible en Ca et P, présentent une balance négative en Ca, due surtout à un excretion fécale plus élevée que les apports. Un rapport inverse est observé entre la balance calcique et l'ingestion alimentaire. L'effet nocif du galactose sur le métabolisme du calcium pourrait agir par l'intermédiaire d'une action sur les cellules osseuses et les fonctions rénales et intestinales, en rapport, peut-être, avec un trouble inconnu du métabolisme hydro-carboné.
    Abstract: Zusammenfassung Die Wirkung von Galaktose auf den Knochenstoffwechsel junger Ratten wurde untersucht, indem diese eine semisynthetische Nahrung erhielten, welche 35% dieses Monosaccharids enthielt. Kontrolltiere erhielten dieselbe Nahrung ohne Galaktose, aber mit Glukose. Die Kontrollgruppe und die Gruppe mit Galaktosenahrung erhielten eine niedrige und eine normal Ca−P-Einnahme. Die Glukose-6-Phosphat-Dehydrogenase des Knochens wurde gehemmt, wenn Galaktose im Gewebe zunahm. Die Urinausscheidung von Calcium, Pyrophosphat, Aminopolysacchariden, Hydroxyprolin und alkalischer Phosphatase des Plasmas (Knochen-Isoenzym) war signifikant höher als bei den Kontrollen. Die Tiere mit Galaktosezusatz und niedriger Ca−P-Aufnahme zeigten eine negative Calciumbilanz, die hauptsächlich durch eine fäkale Ausscheidung bedingt war, welche höher war als die Einnahme. Es wurde eine umgekehrt proportionale Beziehung zwischen Calciumbilanz und Nahrungseinnahme beobachtet. Die nachteilige Wirkung von Galaktose auf den Calciumstoffwechsel mag von einer Wirkung auf die Knochenzellen und auf die Nieren- und Darmfunktion herrühren, vielleicht im Zusammenhang mit einer noch unbestimmten Störung des Kohlenhydratstoffwechsels.
    Notes: Abstract The effect of galactose on bone metabolism was studied by feeding young rats a semisynthetic diet containing 35% of this monosaccharide. Control animals received the same diet without galactose but with glucose. Both a low, and a normal, Ca−P intake were studied in the control and galactose fed groups. Bone glucose-6-phosphate dehydrogenase was inhibited as galactose accumulated in the tissue. Urinary excretion of calcium, pyrophosphate, aminopolysaccharides, hydroxyproline and plasma alkaline phosphatase (bone isoenzyme) were significantly increased above control levels. Galactose fed animals on a low Ca and P diet showed a negative Ca balance, primarily due to a fecal excretion which was greater than intake. An inverse relationship between calcium balance and food intake was observed. The adverse effect of galactose on calcium metabolism may be mediated by an effect on bone cells and on renal and intestinal function, related perhaps to an as yet non-defined disturbance of carbohydrate metabolism.
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  • 18
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    Journal of molecular evolution 2 (1973), S. 251-262 
    ISSN: 1432-1432
    Keywords: Prebiotic Phosphorylation ; Urea ; Struvite ; Ammonium phosphate ; Hydroxylapatite ; Nucleotide ; Pyrophosphate ; Esterification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary When struvite (MgNH4PO4 ⋅ 6H2O) is heated with urea at 65–100°C, inorganic pyrophosphate is formed in good yield. Under similar conditions pyro-phosphate is formed much more slowly from ammonium phosphate or hydroxylapatite. The major products formed by the reaction of nucleotides with urea and either ammonium phosphate or hydroxylapatite are derivatives phosphorylated on the 2′ or 3′ position. With struvite, on the other hand, the main reaction is pyrophosphate bond formation. Yields of up to 25% of uridine diphosphate can be obtained at temperatures as low as 65°C.
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  • 19
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    Calcified tissue international 13 (1973), S. 27-40 
    ISSN: 1432-0827
    Keywords: Pyrophosphate ; Calcium ; Phosphate ; Kinetics ; Hydroxyapatite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'effet du pyrophosphate sur la distribution et les vitesses d'échange du calcium et du phosphate dans les cristaux d'hydroxyapatite a été étudié. Les analyses de disparition du45Ca, du32P [Pi] et du32P [PPi] de la solution vers les cristaux ont été réalisées en utilisant un modèle de compartimenst. Les courbes de disparition sont formées par la somme de 4 exponentielles, correspondant à un modèle de 4 compartiments en séries. Le pyrophosphate est présent dans les 4 compartiments du cristal. Le traitement du cristal avec le pyrophosphate provoque une diminution nette du phosphate échangeable et deux des quatre compartiments disparaissent totalement. Les données quantitatives suggèrent une substitution de 2 moles d'orthophosphate par mole de pyrophosphate. Le pyrophosphate n'a pas d'effet net sur la distribution et les échanges de calcium. Les conséquences de ces résultats sur les effets d'inhibition du pyrophosphate sur la formation et la dissolution des cristaux d'apatite sont discutées.
    Abstract: Zusammenfassung Die Wirkung von Pyrophosphat auf die Verteilung und die Austauschrate von Calcium und Phosphat in Hydroxyapatitkristallen wurde untersucht. Das Verschwinden von45Ca,32P [Pi] und32P [PPi] aus der Lösung und die Anlagerung dieser Ionen auf den Kristallen wurde anhand eines Kompartiment-Modelles studiert. Die Verschwinde-Kurven wurden durch die Summe von 4 Exponentiellen beschrieben und mittels einem Modell von 4 Kompartimenten in Serie interpretiert. Wurde der Lösung Pyrophosphat zugesetzt, so war es in allen 4 Kompartimenten vorhanden. Ferner entstand eine starke Verminderung des austauschbaren Phosphates, wobei 2 der 4 Kompartimente vollständig verschwanden und 2 Mode Orthophosphat mit 1 Mol Pyrophosphat ausgetauscht wurden. Pyrosphosphat hatte keine nennenswerte Wirkung auf die Verteilung und die Flüsse des Calciums. Diese Befunde werden im Zusammenhang mit der Hemmwirkung des Pyrophosphates bei der Bildung und Auflösung von Apatitkristallen besprochen.
    Notes: Abstract The effect of pyrophosphate on the distribution and the rates of exchange of calcium and phosphate in hydroxyapatite crystals was studied. Analysis of disappearance of45Ca,32P [Pi] and32P [PPi] from the solution onto the crystals was performed using a compartmental model. The disappearance curves were described by the sum of 4 exponentials, which was interpreted as a four-compartment model in series. Pyrophosphate was present in all the four pools of the crystals. Treatment of crystal with pyrophosphate led to a large decrease of exchangeable phosphate, and two of the four compartments disappeared completely. The quantitative data suggest a replacement of 2 moles of orthophosphate by 1 mole of pyrophosphate. Pyrophosphate had no appreciable effect on the distribution and the fluxes of calcium. The implications of these results for the inhibitory effects of pyrophosphate on the formation and dissolution of apatite crystals are discussed.
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  • 20
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    Calcified tissue international 10 (1972), S. 128-135 
    ISSN: 1432-0827
    Keywords: Bone ; Embryo ; Calcification ; Phosphate ; Pyrophosphate ; Carbonate ; Apatite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé La maturation chimique et physique du sel osseux est étudiée par l'obervation des caractéristiques stoichiométriques et aux infra-rouges d'os embryonnaire d'oiseaux, du début jusqu'à la fin de la croissance adulte après éclosion. La succession des transformations chimiques de l'os en voie de développement montre surtout un rapport inverse entre le phosphate acide et le carbonate, ainsi que la formation de CO3-apatite. Ces résultats semblent indiquer que le CO 3 2− est substitué au HPO 4 2− au cours de la synthèse du CO3-apatite de l'os.
    Abstract: Zusammenfassung Die chemischen und physikalischen Umwandlungen zum stabilen Knochensalz in Hühnerknochen wurden anhand serienmäßiger Beobachtungen seiner stöchiometrischen Zusammensetzung und seiner infraroten Charakteristika untersucht; diese Beobachtungen erstreckten sich über die Zeit der frühen embryonalen Mineralablagerung bis zur vollständigen Reife nach dem Ausbrüten. Die Sequenz der chemischen Umwandlungen im sich entwickelnden Knochen zeigte hauptsächlich ein entgegengesetztes Verhältnis zwischen saurem Phosphat und Carbonat, das mit der Bildung von Carbonatapatit zusammenfällt. Diese Resultate weisen darauf hin, daß HPO 4 2− bei der Synthese von Carbonatapatit im Knochen durch CO 3 2− substituiert wird.
    Notes: Abstract The chemical and physical maturation of the bone salt was studied by serial observations on its stoichiometric and infrared characteristics in avian bone from early embryonic mineral deposition to full maturity after hatching. The sequence of chemical transformations in the developing bone showed most predominantly an inverse relationship between acid phosphate and carbonate, coincident with the formation of CO3-apatite. The data are consistent with the view that CO 3 2− is substituted for HPO 4 2− in the synthesis of CO3-apatite in bone.
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  • 21
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    Calcified tissue international 10 (1972), S. 302-313 
    ISSN: 1432-0827
    Keywords: Diphosphonates ; Bone resorption ; Mouse ; Pyrophosphate ; Tissue culture ; 45Calcium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Deux diphosphonates, le disodium-éthane-1-hydroxyle-1,1-diphosphonate (EHDP) et le disodium dichlorométhylène diphosphonate (Cl2MDP), inhibent la résorption osseuse, induite par des cellules au niveau de calottes craniennes, cultivées pendant 48 heuresin vitro, lorsque ces substances sont ajoutées au milieu. Le Cl2MDP est plus actif que l'EHDP, à des doses variant 0–16 μg P/ml. Le pyrophosphate et l'imidodiphosphate n'inhibent pas la résorption osseuse à des doses comparables. Lorsque les deux diphosphonates sont injectés à des sourisin vivo avant mise en culture, la résorption osseuse observéein vitro est considérablement réduite: à une dose de 10 μg P/g de poids corporel de Cl2MDP, elle est presque totalement inhibée. Cet effet est rapide et dure plusieurs jours. Les conséquences de ces résultats et la méthode d'essai d'inhibiteurs de la résorption osseuse par la méthode combinéein vivo/ in vitro sont envisagées.
    Abstract: Zusammenfassung Zwei Diphosphonate, Dinatrium-äthan-1-hydroxy-1,1-diphosphonat (EHDP) und Dinatrium-Dichloromethylendiphosphonat (Cl2MDP), hemmen zellbedingte Knochenresorption von Mäuseschädeldächern, welche während 48 Stdin vitro kultiviert worden waren, wenn diese Substanzen dem Nährmedium zugegeben werden. Im Dosierungsbereich von 0–16 μg P/ml ist Cl2MDP wirksamer als EHDP. Pyrophosphat und Imidodiphosphat blockieren die Knochenresorption bei entsprechenden Dosen nicht. Wenn die zwei Diphosphonate Mäusenin vivo injiziert werden, bevor das Explantat hergestellt wird, ist die nachfolgende Knochenresorptionin vitro stark vermindert; bei einer Dosierung von 10 μg P/g Körpergewicht von Cl2MDP ist die Resorption fast gänzlich blockiert. Diese Wirkung erfolgt rasch und dauert während einigen Tagen an. Die Folgerungen aus diesen Ergebnissen sowie das Verfahren, Knochenresorptionshemmer mittels kombinierterin vivo/in vitro-Methode zu prüfen, werden diskutiert.
    Notes: Abstract Two diphosphonates, disodium ethane-1-hydroxy-1,1-diphosphonate (EHDP) and disodium dichloromethyle diphosphonate (Cl2MDP), inhibit cell-mediated bone resorption of mouse calvaria cultivated for 48 hoursin vitro, when the compounds are added to the medium. Cl2MDP is more effective than EHDP over the dose range 0–16 μg P/ml. Pyrophosphate and imidodiophosphate do not block bone resorption at comparable dose levels. When the two diphosphonates are injected into micein vivo before explants are prepared, subsequent bone resorptionin vitro is considerably reduced; at a dose level of 10 μg P/g body weight of Cl2MDP it is almost completely blocked. This effect is rapid and persists for several days. The implications of these results and the method of testing inhibitors of bone resorption by the combinedin vivo/in vitro method are discussed.
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  • 22
    ISSN: 1432-0827
    Keywords: Pyrophosphate ; Bone ; Cartilage ; Calcification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les concentrations de pyrophosphate inorganiques (PPi), d'orthophosphate et de calcium ont été déterminées dans le cartilage au repos, en prolifération, hypertrophique et calcifié au niveau d'épiphyses foetales de veaux et aussi dans l'os spongieux, périosté et compact. Dans les échantillons de cartilage, le contenu en PPi augmente progressivement dans l'ordre énoncé ci-dessus, de 8.59 μg P/g en poids sec de cartilage au repos à 236 μg P/g en poids sec dans le cartilage calcifié. Cependant, le rapport PPi sur orthophosphate suit une relation inverse: il est plus élevé dans la zone de repos et diminue considérablement lorsque le tissu se calcifie. Le rôle possible du PPi, en inhibant la précipitation de phosphate de calcium amorphe (ACP) et en ralentissant la transformation d'ACP en hydroxyleapatite (HA) dans les tissus calcifiés, est envisagé par rapport à d'autres facteurs, tels que le collagène, le magnésium, les phospholipides et les protéines-polysaccharides, qui peuvent aussi intervenirin vivo. Pour l'instant, aucun facteur isolé ne peut être considéré comme un régulateur physiologique certain.
    Abstract: Zusammenfassung Der Gehalt an anorganischem Pyrophosphat (PPi), Orthophosphat und Calcium wurde in ruhendem, proliferierendem, hypertrophischem und verkalktem Knorpel von foetalen Kalbsepiphysen und auch in spongiösem, periostalem und kompaktem Knochen gemessen. Bei den Knorpelproben nahm der Gehalt an PPi progressiv in der oben angegebenen Reihenfolge zu: von 8,59 μg P/g Trockengewicht in ruhendem Knorpel bis zu 236 μg P/g Trockengewicht in verkalktem Knorpel. Das PPi/Orthophosphat-Verhältnis hingegen verlief in umgekehrter Richtung; es war am höchsten in der ruhenden Zone und nahm dramatisch ab, wenn das Gewebe verkalkte. Die mögliche Rolle von PPi bei der Hemmung der Ausfällung von amorphem Calciumphosphat (ACP) und bei der Verlangsamung der Umwandlung von ACP in Hydroxyapatit (HA) in verkalkenden Geweben wird in bezug auf folgende anderen Faktoren, welche den Vorgang in vivo ebenfalls beieinflussen könnten, diskutiert: Collagen, Magnesium, Phospholipide und Proteinpolysaccharide. Bis jetzt war es nicht möglich, einen einzelnen Faktor als sicheren physiologischen Regulator zu identifizieren.
    Notes: Abstract The amounts of inorganic pyrophosphate (PPi), orthophosphate and calcium have been measured in resting, proliferating, hypertrophic and calcified cartilage from foetal calf epiphyses and also in cancellous, periosteal and compact bone. In the cartilage samples, the content of PPi increased progressively in the order named above, from values of 8.59 μg P/g dry weight in resting cartilage to 236 μg P/g dry weight in calcified cartilage. However, the ratio of PPi to orthophosphate followed the reverse relationship and was highest in the resting zone and fell dramatically as the tissue calcified. The possible role of PPi in inhibiting the precipitation of amorphous calcium phosphate (ACP) and in the slowing the transformation of ACP to hydroxyapatite (HA) in calcifying tissues is discussed in relation to other factors, such as collagen, magnesium, phospholipids and proteinpolysaccharides, which might also influence the processin vivo. At present, no single factor can be identified as a proven physiological regulator.
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  • 23
    ISSN: 1432-0827
    Keywords: Pyrophosphate ; Cyclic 3′5′-AMP ; Parathyroid ; Adenyl cyclase ; Bone ; Resorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'injection de pyrophosphate inorganique, à la concentration de 15 μmoles/h, au niveau de rats thyro-parathyréodectomisés, inhibe les effects de l'hormone parathyroidienne injectée, sur le calcium et le phosphate plasmatique et sur l'excrétion rénale du calcium, du phosphate, des peptides contenant l'hydroxyproline et de l'AMP 3′5′ cyclique. Inversement, l'injection de pyrophosphate ne provoque pas de changements significatifs sur les effects d'injection d'AMP 3′5′ cyclique sur le calcium et le phosphate du plasma, ou sur l'excrétion urinaire de calcium, phosphate et peptides contenant de l'hydroxyproline.
    Abstract: Zusammenfassung Wurde thyroparathyreoidektomierten Ratten anorganisches Pyrophosphat mit einer Geschwindigkeit von 15 μMol/Std infundiert, so blockierte dies die Wirkung der gleichzeitig laufenden Parathormoninfusion auf Plasmacalcium und-phosphat, sowie auf die renale Ausscheidung von Calcium, Phosphat, Hydroxyprolin-haltigen Peptiden und cyclischem 3′,5′-AMP. Hingegen bewirkte die Pyrophosphatinfusion keine signifikante Veränderung der Wirkung einer Infusion von zyklischem 3′,5′-AMP auf Plasmacalcium und-phosphat oder auf die Ausscheidung im Urin von Calcium, Phosphat und Hydroxyprolin-haltigen Peptiden.
    Notes: Abstract The infusion of inorganic pyrophosphate at a rate of 15 μmoles/h into thyroparathyroidectomized rats blocked the effects of parathyroid hormone infusion upon plasma calcium and phosphate, and upon the renal excretion of calcium, phosphate, hydroxyproline-containing peptides, and cyclic 3′5′ AMP. In contrast, pyrophosphate infusion caused no significant change in the effects of cyclic 3′5′ AMP infusion upon plasma calcium and phosphate, or upon the urinary excretion of calcium, phosphate, and hydroxyproline-containing peptides.
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  • 24
    ISSN: 1432-0827
    Keywords: Pyrophosphate ; Orthophosphate ; Phosphonates ; Phosphates ; Parathyroid ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Lors d'essais précédents, nous avons montré que le pyrophosphate minéral (PPi) inhibe in vitro la dissolution de cristaux d'hydroxyapatite et nous avons suggéré que le PPi pourrait être un régulateur physiologique de la résorption osseuse. Dans ce travail, nous avons cherché si le PPi ainsi que d'autres produits phosphorés ont une action inhibitrice sur la résorption osseuse induite par l'hormone parathyroïdienne dans des calottes craniennes de souris et sur l'augmentation du calcium plasmatique induite par l'hormone parathyroïdienne chez des rats thyroparathyroïdectomisés maintenus en régime déficient en calcium. Ni l'orthophosphate, ni le pyrophosphate, ni les polyphosphates, ni deux phosphates polymérisés, inhibiteurs des phosphatases, n'ont inhibé la résorption des calottes craniennes, ni l'augmentation du calcium plasmatique. Par contre, certains phosphonates, contenant la liaison P-C-P, ont réduit la dissolution in vitro de cristaux d'hydroxyapatite et inhibé la résorption osseuse en culture de tissus à une concentration aussi faible que 1,6×10−6 molaire. Certains diphosphonates ont inhibé également l'augmentation du calcium plasmatique chez des rats thyroparathyroïdectomisés. La différence d'activité des produits contenant la liaison P-O-P ou P-C-P peut être attribuée à une plus grande résistance des derniers à une hydrolyse chimique ou enzymatique. Les phosphonates peuvent servier de modèle pour étudier l'action du PPi endogène de l'os. Ils peuvent également être utiles pour éclaircir le mécanisme de la formation et de la destruction osseuse et pourraient jouer un rôle dans la thérapie des maladies présentant une résorption osseuse accrue.
    Abstract: Zusammenfassung Frühere Untersuchungen zeigten, daß anorganisches Pyrophosphat (PPi) die Auflösung von Hydroxyapatit-Kristallenin vitro hemmt; es wurde vorgeschlagen, daß PPi physiologisch die Knochenresorption regulieren könnte. Bei diesem Versuch wurden PPi und andere Phosphatderivate auf ihre Eignung geprüft, die Knochenresorption zu hemmen, welche an Mäusecalvarien durch Parathormon hervorgerufen wurde; ebenso wurde abgeklärt, ob diese Substanzen in thyroparathyreoidektomierten, auf calciumarmer Diät gehaltenen Ratten in der Lage waren, den durch Parathormongaben verursachten Blutcalciumanstieg zu hemmen. Weder Orthophosphat, noch Pyrophosphat, Polyphosphat und zwei polymere Phosphatinhibitoren der Phosphatasen konnten die Resorption von Calvarien oder den Anstieg des Plasmacalciums hemmen. Dagegen verzögerten verschiedene Phosphonate mit P-C-P-Bindungen die Auflösung von Hydroxyapatitin vitro und hemmten dazu in so tiefen Konzentrationen wie 1,6×10−6M die Knochenresorption in der Gewebezucht. Einige Diphosphonate hemmten auch den Plasmacalciumanstieg bei thyroparathyreoidektomierten Ratten. Eine Ursache der unterschiedlichen Wirksamkeit von Substanzen, welche P-O-P- oder P-C-P-Bindungen enthalten, kann darin liegen, daß die letztgenannten einen größeren Widerstand gegenüber chemischer und enzymatischer Hydrolyse entgegenbringen. Phosphonate könnten als Model für die Wirkung des endogenen PPi im Knochen dienen und zudem zur Erläuterung der Mechanismen von Knochenbildung und-resorption nützlich sein; sie könnten auch zur Therapie jener Krankheiten, die eine erhöhte Knochenresorption zur Folge haben, herangezogen werden.
    Notes: Abstract Earlier studies have shown that inorganic pyrophosphate (PPi) inhibits the dissolution of hydroxyapatite crystalsin vitro and it has been suggested that PPi might be a physiological regulator of bone resorption. In this study PP1 and other phosphate compounds have been tested for their ability to inhibit bone resorption induced by parathyroid hormone in mouse calvaria and to inhibit the rise in plasma calcium induced by parathyroid hormone in thyroparathyroidectomised rats on a low calcium diet. Orthophosphate, pyrophosphate, polyphosphate and two polymeric phosphate inhibitors of phosphatases did not inhibit the resorption of calvaria or the rise in plasma calcium. In contrast, several phosphonates containing P-C-P bonds retarded the dissolution of hydroxyapatite crystalsin vitro, and, at concentrations down to 1.6×10−6M, inhibited bone resorption in tissue culture. Some diphosphonates also inhibited the rise in plasma calcium in thyroparathyroidectomised rats. One reason for the difference between the effects of compounds containing P-O-P and P-C-P bonds may be related to the greater resistance of the latter to chemical and enzymic hydrolysis. Phosphonates may provide a model for the effect of endogenous PP1 in bone, and might be of use in elucidating provide a model for the effect of endogenous PP1 in bone, and might be of use in elucidating mechanisms of bone formation and resorption and in the therapy of diseases that involve increased resorption of bone.
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  • 25
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    Calcified tissue international 4 (1969), S. 231-244 
    ISSN: 1432-0827
    Keywords: Calcification ; Pyrophosphate ; Inhibitors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les propriétés d'induction de calcification des liquides biologiques peuvent être mesurées, in vitro et in vivo, par leur possibilité de redurcir des blocs d'émail décalcifié. Cette propriété est exprimée par les concentrations de calcium (et de phosphate) de solutions synthétiques inductrices de calcification, de concentrations et d'activité connues. Un plasma humain typique a une activité inductrice correspondant à celle d'une solution contenant du calcium, 0,70 mM, Ca/P, 1,67 et fluorure, 0,05 mM. L'activité relativement peu élevée des sérums et des plasmas s'explique par la présence d'inhibiteurs ioniques. L'ion phosphate est l'un d'eux, mais ne peut rendre compte de l'inhibition totale. Des anions et des cations sont responsables de l'inhibition, avec un rôle majeur pour les cations. Les ions suivants, en concentration physiologique, jouent un rôle inhibiteur: P7O 7 4− , HCO 3 − , SiO 4 2− , CrO 4 2− , Mg2+, Zn2+. Un mélange de ces ions provoque une inhibition totale identique à celle du plasma.
    Abstract: Zusammenfassung Der Einfluß biologischer Flüssigkeiten auf den Verkalkungsvorgang kann in vitro und in vivo anhand ihrer Fähigkeit, enthärtete Blöcke von Zahnschmelz wieder zu härten, gemessen werden. Diese Aktivität wird ausgedrückt als Konzentration des Calciums (und Phosphates) synthetischer calcifizierender Lösungen mit bekannter Konzentration und Aktivität. Die Aktivität eines charakteristischen menschlichen Plasmas entsprach derjenigen einer Lösung folgender Zusammensetzung: Calcium 0,70 mM; Ca/P=1,67 und Fluorid 0,05 mM. Die relativ niedrige Aktivität von Serum und Plasma ist bedingt durch das Vorhandensein einer Anzahl ionischer Inhibitoren. Das Pyrophosphation ist ein solcher; er kann aber nicht für die gesamte Inhibition verantwortlich gemacht werden. Sowohl anionische als auch kationische Inhibitoren sind vorhanden, wobei die Kationen den Hauptanteil ausmachen. Folgende Ionen erwiesen sich in einer physiologischen Konzentration als Inhibitoren synthetischer Systeme: P7O 7 3− , HCO 3 − , SiO 4 1− , CrO 4 2− , Mg2+, Zn2+. Zusammengenommen verursachten diese Ionen eine Gesamtinhibition ähnlich derjenigen des Plasmas.
    Notes: Abstract The calcifying activities of biological fluids can be measured,in vitro andin vivo, by their ability to reharden softened blocks of tooth enamel. The activity is expressed in terms of the calcium (and phosphate) concentrations of synthetic calcifying solutions of known concentration and activity. A typical human plasma had an activity corresponding to that of a solution of the following concentration: calcium, 0.70 mM; Ca/P, 1.67 and fluoride, 0.05 mM. The relatively low activity of serums and plasmas was shown to arise from the presence of a number of ionic inhibitors. Pyrophosphate ion is one such inhibitor but cannot account for the major inhibition. Both anionic and cationic inhibitors were shown to be present, with the cations respresenting the major portion. The following ions at their reported physiological concentration were shown to be inhibitors in synthetic systems: P7O 7 4− , HCO 3 − , SiO 4 2− , CrO 4 2− , Mg2+, Zn2+. In combination, these ions caused a total inhibition similar to those for plasmas.
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  • 26
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    Calcified tissue international 3 (1969), S. 284-292 
    ISSN: 1432-0827
    Keywords: Hydroxyapatite ; Pyrophosphate ; Nucleotides ; Adenosine triphosphate ; Transphosphorylation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé La base de la transphosphorilation entre les nucléotides et l'hydroxyapatite (HA) est explorée. Utilisant un recent modèle de la surface de HA et de la structure de polyphosphates de 2 et 3 parties, une raisonnable explication atomique peut être montrée pour cette réaction. La transphosphorilation a produit un pyrophosphate sur HA qui est différent du pyrophosphate absorbé sur HA de la solution. Les modèles suggèrent que la distinction est dûe à une orientation différente du pyrophosphate sur la surface de HA dépendant de l'origine du pyrophosphate.
    Abstract: Zusammenfassung Es wurde die Grundlage für die Transphosphorylierung zwischen Nukleotiden und Hydroxy-Apatit (HA) untersucht. Eine plausible atomare Darstellung dieser Reaktion ist möglich, wenn man kürzlich vorgeschlagene Modelle der Oberfläche von HA und der Struktur von zwei- und dreigliedrigen Polyphosphaten benutzt. Man findet dann, daß Transphosphorylierung zu einem Pyrophosphat des HA führt, welches von dem Pyrophosphat, welches HA aus der Lösung absorbiert, unterschieden werden kann. Auf Grund der Modelle kann man annehmen, daß dieser Unterschied auf einer unterschiedlichen Orientierung des Pyrophosphats auf der Oberfläche des HA beruht, welche wiederum von der Herkunft des Pyrophosphats abhängt.
    Notes: Abstract The basis for transphosphorylation between nucleotides and hydroxyapatite (HA) has been explored. Using a recently-proposed model for the surface of HA and the structure of 2- and 3-membered polyphosphates, a reasonable atomic explanation can be shown for this reaction. Transphosphorylation has been found to result in a pyrophosphate on HA which is distinctive from pyrophosphate absorbed onto HA from solution. The models suggest that this distinction is due to a different orientation of the pyrophosphate on the surface of the HA depending on the origin of the pyrophosphate.
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  • 27
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 3 (1969), S. 318-326 
    ISSN: 1432-0827
    Keywords: Osteogenesis Imperfecta ; Pyrophosphate ; Magnesium ; Pyrophosphatase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Du collagène osseux provenant de fragments d'ostéogenèse imparfaite est un puissant inhibiteur de la calcificationin vitro. Cet effet inhibiteur peut être supprimé par traitement du collagène à la pyrophosphatase en présence d'ions de magnésium. Des concentrations élevées de pyrophosphates inorganiques sérique et urinaire ont été observées chez 28 malades atteints d'ostéogenèse imparfaite. L'administration buccale d'oxyde de magnésium ou de sulfate de magnésium à quatre de ces malades diminue de façon significative la quantité des pyrophosphates sérique et urinaire.
    Abstract: Zusammenfassung Der Knochenkollagen von Osteogenesis imperfecta-Kranken ist ein mächtiger Hemmstoff für die Verkalkung in vitro. Die Inhibition wird durch Behandlung des Kollagens mit Pyrophosphatase in Anwesenheit von Magnesiumionen aufgehoben. Erhöhte Spiegel von anorganischem Pyrophosphat wurden im Urin und im Serum von 28 Kranken mit Osteogenesis imperfecta gefunden. Wurden 4 Patienten mit peroralen Gaben von Magnesiumoxyd oder Magnesiumsulfat behandelt, so verminderte sich der Pyrophosphatspiegel im Serum und im Urin signifikant.
    Notes: Abstract The bone collagen of human osteogenesis imperfecta is a potent inhibitor ofin vitro calcification. The inhibition was removed by treatment of the collagen with pyrophosphate in the presence of magnesium ions. Elevated levels of serum and urinary inorganic pyrophosphate were found in 28 patients with osteogenesis imperfecta. Oral administration of magnesium oxide or magnesium sulfate to four of these patients significantly reduced their serum and urinary levels of pyrophosphate.
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  • 28
    ISSN: 1432-0827
    Keywords: Pyrophosphate ; Calcium Phosphate ; Phosphatase ; Crystallization ; Pyrophosphatase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé La transformation du phosphate calcique de la forme amorphe en forme cristalline a été étudiéein vitro dans différentes conditions. On a suivi cette transformation en étudiant la variation des paramètres suivants: le pH de la solution et sa teneur en calcium et en phosphate, ainsi que le rapport Ca/P et la courbe de diffraction aux rayons X de la phase solide. Le pyrophosphate inorganique augmente sensiblement le temps nécessaire à cette transformation dans les différentes conditions choisies. Cet effet s'annule lorsqu'on ajoute en plus du pyrophosphate de la phosphatase alcaline intestinale. Les auteurs suggèrent que le pyrophosphate pourrait être l'un des facteurs qui permettent à une partie du minéral de l'os de demeurer dans un état non-cristallin. La phosphatase alcaline de l'os, grâce à son activité pyrophosphatasique, serait capable d'accélérer cette transormationin vivo.
    Abstract: Zusammenfassung Die Umwandlung von amorphem in kristallines Calciumphosphat wurdein vitro unter verschiedenen Bedingungen studiert. Diese Umwandlung wurde folgendermaßen verfolgt: einerseits in der Lösung durch Änderung des pH's und des Calcium- und Phosphatgehaltes, andererseits in der soliden Phase durch Änderung des Ca/P-Verhältnisses, sowie des Röntgenstrahlendiffraktionsbildes. Es konnte festgestellt werden, daß unter den verschiedenen Versuchsbedingungen die Anwesenheit von anorganischem Pyrophosphat die zur Umwandlung benötigte Zeit wesentlich verlängert. Wird noch intestinale alkalische Phosphatase zugesetzt, so wird die durch das Pyrophosphat verlängerte Umwandlungszeit aufgehoben. Es wird vorgeschlagen, daß Pyrophosphat einer der Faktoren sein kann, der Teile des Knochenminerals in einem nicht kristallinen Zustand verbleiben läßt. Die alkalische Knochen-phosphatase könnte, dank ihrer Pyrophosphataseaktivität, eine Beschleunigung des Umwandlungsprozessesin vivo ermöglichen.
    Notes: Abstract The transformation of amorphous calcium phosphate into its crystalline form has been studiedin vitro under various conditions. The transformation was followed by changes in the pH and in the calcium and phosphate content of the solution and by changes in the Ca/P ratio and x-ray diffraction patterns of the solid phase. It was found that inorganic pyrophosphate markedly increased the time required for the transformation under the various conditions used. The addition of intestinal alkaline phosphatase abolished this retarding effect of pyrophosphate on the transformation. It is proposed that pyrophosphate may be one of the factors that allows part of the bone mineral to persist in a non-crystalline state. The alkaline phosphatase of bone, by virtue of its pyrophosphatase activity, might be able to accelerate the transformation processin vivo.
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