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111.
The stability constants of the ternary complexes containing UTP, 2,2′-bipyridyl (bipy), and Co2+, Ni2+, Cu2+, or Zn2+ (M2+) have been determined by potentiometric titrations (Table 1). Changes in stability are quantified by Δlog KM = log K–log K. For the Co2+, Ni2+, Cu2+, and Zn2+ systems Δlog KM is 0.10, ?0.13, 0.36, and 0.15, respectively. All these ternary complexes are considerably more stable than would be expected on statistical grounds; indeed, for Co2+, Cu2+, and Zn2+, UTP4? binds more tightly to M (bipy)2+ than to M2+. An UV. difference spectroscopic study suggests that stacked adducts between bipyridyl and the pyrimidine moiety of uridine are formed. 1H-NMR. studies of the bipy/uridine, bipy/UTP, and bipy/UTP/Zn2+ systems (Figs. 1 and 2) confirm the presence of stacking in the binary adducts and in the ternary complex. There is also evidence for the existence of the stacked protonated complex, Zn(bipy) (HUTP)?, with the proton at the γ-phosphate group. The acidity constant of this ternary complex has been measured (Fig. 3). The observed stability enhancement of stacked adducts by the formation of a metal ion bridge is discussed (Fig. 4) and biological implications are indicated. 相似文献
112.
Helmut Trutnovsky 《Fresenius' Journal of Analytical Chemistry》1963,198(4):331-344
Summary An automatic micro-determination of nitrogen by combustion of the sample in pure oxygen is described. The oxygen is generated during the combustion in an electrolytic generator, the flow of carbon dioxide being cut off by a magnetic valve. After four minutes of combustion an automatic change-over from oxygen to carbon dioxide is performed. The excess of oxygen is bound by a layer of copper which also reduces the nitrogen oxides. This copper is suitable for 60–80 determinations. It is contained in a detachable part of the combustion tube and thus can be easily exchanged when being exhausted. The use of pure oxygen instead of a mixture with carbon dioxide extends the life time of the copper layer with the same quantity of oxygen pro analysis. As neither the combustion nor the sweeping of the tube need any attendance, a determination can be performed within eight minutes.
Der Fa. Novo Terapeutisk A/S sei an dieser Stelle für die Erlaubnis der Veröffentlichung und Frl. L. Sørensen für die Durchführung zahlreicher Analysen herzlich gedankt. 相似文献
Der Fa. Novo Terapeutisk A/S sei an dieser Stelle für die Erlaubnis der Veröffentlichung und Frl. L. Sørensen für die Durchführung zahlreicher Analysen herzlich gedankt. 相似文献
113.
Helmut Pfitzner und Helmut Schweppe 《Fresenius' Journal of Analytical Chemistry》1974,268(5):337-342
Zusammenfassung In einer früheren Veröffentlichung [4] ist auf die Möglichkeit der chromatographischen Trennung strukturisomerer Metallchelate hingewiesen worden; sie soll hier ausführlicher dargestellt werden. Weiterhin wird die Trennung von 1:2-Mischkomplexen von Azofarbstoffen und von 1:2-Metallkomplex-Mischungen durch Dünnschicht-Chromatographie (DC) an Polyamid beschrieben. Unter bestimmten Voraussetzungen kann durch DC an Kieselgel zwischen 1:2-Metallkomplexfarbstoffen mit Sulfonsäureamid- bzw. Alkylsulfongruppen und solchen ohne diese Substituenten unterschieden werden. Die beschriebenen DC-Methoden ermöglichen bei richtiger Interpretation eine eindeutige Unterscheidung zwischen strukturisomeren Metallkomplexen der 1:1- und 1:2-Reihe, sowie Mischkomplexen und Komplexmischungen vom 1:2-Metall-chelattyp unsulfierter o,o-Dihydroxyazoverbindungen.Symmetrische o,o-Dihydroxyazoverbindungen, wie z.B. das 2,2-Dihydroxy-5,5-dimethyl-azobenzol(7), sind geeignete Komplexbildner für Schwermetallkationen, um diese als farbige Chelate mit Hilfe der DC voneinander zu trennen. Strukturisomere sind wegen der Molekülsymmetrie ausgeschlossen, so daß die Ergebnisse eindeutig sind.
1:1 and 1:2 metal chelates of unsulphonated o,o-dihydroxyazo compounds: A thin-layer chromatographic investigation
In an earlier publication [4] the possibility of the Chromatographic separation of structurally isomeric metal chelates was mentioned; this is dealt with here in more detail. Further the separation of 1:2 mixed complexes from azo dyes and 1:2 metal-complex mixtures by thin-layer chromatography (TLC) on polyamide is described. In certain circumstances it is possible to distinguish between 1:2 metal-complex dyes with sulphonamide or alkylsulphonyl groups and those without these substituents by TLC on silica gel. The TCL methods described allow-when correctly interpreted-an unambiguous distinction between structurally isomeric metal complexes of the 1:1 and 1:2 series, and mixed complexes and mixtures of complexes of the 1:2 metal-chelate type of unsulphonated o,o-dihydroxyazo compounds.Symmetrical o,o-dihydroxyazo compounds, such as 2,2-dihydroxy-5,5-dimethylazobenzene(7), are suitable as complex-formers for heavy-metal ions, allowing the separation of the latter as their coloured chelates with aid of TLC. Structural isomers are excluded because of the molecular symmetry, so that the results are unambiguous.相似文献
114.
Helmut Link 《Helvetica chimica acta》1978,61(7):2419-2427
Synthesis of 1,3,4-Oxadiazoles and 4,5-Dihydro-l,2,4-triazines from 3-Dimethylamino-2,2-dimethyl-2 Hazirine and Carbohydrazides 3-Dimethylamino-2, 2-dimethyl-2 H-azirine ( 1 ) reacts with aromatic carbohydrazides to give 2-(1-amino-1-methylethyl)-5-aryl-1, 3, 4-oxadiazoles ( 7 , 10 , 11 ). With ethyl carbazate the azirine 1 forms the aminoester 15 , which is easily cyclized to the 4, 5-dihydro-1, 2, 4-triazin-3 (2H)-one 16 . From the reaction of 1 with oxamohydrazide ( 17 ) and oxalodihydrazide 19 the 4, 5-dihydro-1, 2, 4-triazin-3-carboxamide 18 and the symmetric compound 20 , respectively, have been isolated. Reactions supporting the structures of the new compounds are described. 相似文献
115.
Helmut Bahrmann Klaus Bergrath Han -Jerg Kleiner Peter Lappe Christoph Naumann Dieter Peters Dieter Regnat 《Journal of organometallic chemistry》1996,520(1-2):97-100
BINAS is a new, very efficient ligand for propylene hydroformylation. BINAS is made by the sulfonation of NAPHOS. Different synthetic routes to NAPHOS are discussed. A new two step synthesis starting from 2,2′-bis(bromomethyl)-1,1′-binaphthyl is described. 相似文献
116.
Helmut Viernstein Petra Weiss-Greiler Peter Wolschann 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):235-240
The solubility enhancement of triflumizole by complexation with -cyclodextrin and with dimethyl--cyclodextrin is compared with respect to the different physico-chemical properties of the host molecules. Although the inclusion reaction constants are rather similar for both complexation reactions, a completely different temperature dependence of the host-guest interaction is observed, which indicates a change of the reaction mechanisms. Moreover, the influence of ethanol as cosolvent is studied. 相似文献
117.
A New Approach to Bicyclo[4.1.0]heptane Derivatives The reaction of the dienone 1 with ethyl α-bromoacetate does not furnish the expected glycidic acid ester 2 but leads to the bicyclo[4.1.0]heptenone derivative 3 . The structure of this new compound has been proved by means of spectroscopic methods (1R, 1H-NMR, 13C-NMR, MS). The elucidation of the configuration at C(7) could be realized by measuring a NOE effect. Other α-alkylated α-bromoacetates react with 1 in the same manner. 相似文献
118.
Helmut Siemon 《Journal of Geometry》1984,23(1):83-93
In the affine plane over a Galois field GF(q), q ; 3(4), q = p, of congruence transformations, of motions and of the generation of all point reflections respectively. Then we determine the groups AutC, AutM, AutM and obtain the following results: 1. Aut C is isomorphic to the product of the augmented group of similarities (generated by similarities, quasi reflections, quasi rotations 2) and the group of collineations which are induced by the automorphism of GF(q) operating on the coordinates. 2. AutM– AutC. 3. AutM– group of affinities of the affine space of dimension 2 over the prime field. 4. Moreover for any desarguesian affine plane Aut Dil (Dil = group of dilatations) is isomorphic to (the full collineation group).Lecture delivered at the Haifa Geometry conference 1983In my lecture I called these transformations semi-. To avoid confusion I follow here a suggestion of E. Schröder. 相似文献
119.
Helmut Knebl 《manuscripta mathematica》1984,49(2):165-175
Let p,q be relatively prime integers with 2pr
p,q
be the numerical semigroup generated by p,q,{(p–1) (q–1)–1–(ip+jq)¦i+jr–2}. Then there exists a smooth projective curve X and a point x on X, such that H
r
p,q
is the set of orders of poles of the rational functions on X, which are regular on X\{x}; in other words: H
r
p,q
is a Weierstraß semigroup. 相似文献
120.
Superstructures of temporarily stabilized nanocrystalline CaCO3 particles: morphological control via water surface tension variation 总被引:1,自引:0,他引:1
In this paper, the formation of different complex morphologies of nanocrystalline CaCO3 under the control of double hydrophilic block copolymers (DHBCs) carrying phosphate groups is described. The DHBCs consist of a poly(ethylene glycol) (PEG) block and a pendant poly[2-(2-hydroxy ethyl)ethylene] block with different degrees of phosphorylation up to 40%, some of which show surface activity. The polymers furthermore temporarily stabilize CaCO3 nanocrystals, which are formed by slow CO2 evaporation from a supersaturated Ca(HCO3)2 solution (Kitano method). The polymers are active down to concentrations of 10(-4) g/L. In dependence of the nature and concentration of the DHBC, tunable complex shuttlecock flowerlike and other superstructures are formed, which are aggregates of CaCO3 vaterite nanoparticles with an enhanced stability of at least 2 months. It is shown that the aggregation starts around template CO2 gas bubbles at the air/water interface. The size and morphology of the growing aggregates depends on the polymer concentration, phosphorylation degree, and water surface tension. The latter determines when the aggregate sinks to the bottom, interrupting the further growth process. Variation of the water surface tension by addition of the nonionic surfactant Antharox CO880 also allows a variation of the aggregate morphology, thus implying the described method as simple and versatile for the generation of complex CaCO3 morphologies. 相似文献