Strongly countable dimensional compacta form the Hurewicz set

The hyperspaces of strongly countable dimensional compacta of positive dimension and of strongly countable dimensional continua of dimension greater than 1 in the Hilbert cube are homeomorphic to the Hurewicz set of all nonempty countable closed subsets of the unit interval [0,1]. These facts hold true, in particular, for covering dimension dim and cohomological dimension dimG, where G is any Abelian group.     

The emergence of background geometry from quantum fluctuations

We show how the quantization of two-dimensional gravity leads to an (Euclidean) quantum space–time where the average geometry is that of constant negative curvature and where the Hartle–Hawking boundary condition arises naturally.     

Komplexbildende Eigenschaften des 3,5-Dimethylpyrazols

Zusammenfassung 3,5-Dimethylpyrazol bildet in Anwesenheit von Rhodanid mit Kupfer(II) einen gefärbten Komplex, der in Chloroform leicht löslich ist. Diese Reaktion wurde zur photometrischen Bestimmung von 10 bis 100g Cu/5 ml verwendet.

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Summary A colored complex, that is readily soluble in chloroform, is formed by copper(II) with 3,5-dimethylpyrazole in the presence of thiocyanate. This reaction was employed for the photometric determination of 10 to 100g Cu/5 ml.

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Résumé Le diméthyl-3,5 pyrazol forme avec le cuivre-II en présence de thiocyanate, un complexe coloré, facilement soluble dans le chloroforme. On a utilisé cette réaction pour le dosage photométrique de 10 à 100g Cu/5 ml.

     

N‐Acetyl‐l‐tyrosine methyl ester monohydrate at 293 and 123 K

The crystal structure of a protected l ‐tyrosine, namely N‐acetyl‐l ‐tyrosine methyl ester monohydrate, C₁₂H₁₅NO₄·H₂O, was determined at both 293 (2) and 123 (2) K. The structure exhibits a network of O—H...O and N—H...O hydrogen bonds, in which the water molecule plays a crucial role as an acceptor of one and a donor of two hydrogen bonds. Molecules of water and of the protected l ‐tyrosine form hydrogen‐bonded layers perpendicular to [001]. C—H...π interactions are observed in the hydrophobic regions of the structure. The structure is similar to that of N‐acetyl‐l ‐tyrosine ethyl ester monohydrate [Soriano‐García (1993). Acta Cryst. C 49 , 96–97].     

Comparison of calorimetry and neutron scattering results concerning phase transitions in /Ni(NH3)6/(NO3)2 with the raman band profile study

Previously obtained calorimetry results revealed an existance of three solid phases in /Ni(NH₃)₆/(NO₃)₂. Neutron quasielastic scattering results, also obtained previously, gave evidence of quick reorientations of NH₃ groups around NiN axes in phases I and II. In the Raman profile study now reported we show that the NO^?₃ groups reorient quickly in phase I, whereas they are fixed in phase II. Connection of NH₃ and NO^?₃ reorientations with entropy of I?II transition is discussed.     

Cationic Heteroconjugation Constants in the OHN+ and NHO+ Systems in Propylene Carbonate: Dependence on Difference in Basicity

Cationic heteroconjugation equilibria of more than ninety systems consisting of substituted pyridines, their N-oxides, and trimethylamine N-oxide, i. e., in systems with mixed hydrogen bridges of type OHN⁺ (NHO⁺) were studied in propylene carbonate. Both experimental systems without proton transfer, BH⁺/B₁, and those with proton transfer, B₁H⁺/B, were explored. The stability of the mixed hydrogen bridges, OHN⁺ (NHO⁺), is compared with that of the OHC⁺-type bridges. The influence of the difference in basicity of the conjugate base of the proton donor and the proton acceptor on the presence of the proton transfer equilibria, and, consequently, the possibility of determination of the cationic heteroconjugation constant values is discussed.     

Mechanistic studies on the binding of nitric oxide to a synthetic heme-thiolate complex relevant to cytochrome p450

The synthetic heme-thiolate complex (SR) in methanol binds nitric oxide (k(on) = (2.7 +/- 0.2) x10(6) M(-)(1) s(-)(1) at 25 degrees C) to form SR(NO). The binding of NO to the SR complex in a noncoordinating solvent, such as toluene, was found to be almost 3 orders of magnitude faster than that in methanol. The activation parameters DeltaH(), DeltaS(), and DeltaV() for the formation of SR(NO) in methanol are consistent with the operation of a limiting dissociative mechanism, dominated by dissociation of methanol in SR(MeOH). In the presence of an excess of NO, the formation of SR(NO) is followed by subsequent slower reactions. The substantially negative activation entropy and activation volume values found for the second observed reaction step support an associative mechanism which involves attack of a second NO molecule on the thiolate ligand in the initially formed SR(NO) complex. The following slower reactions are strongly accelerated by a large excess of NO or by the presence of NO(2)(-) in the SR/NO reaction mixture. They can be accounted for in terms of dynamic equilibria between higher nitrogen oxides (NO(x)()) and reactive SR species, which lead to the formation of a nitrosyl-nitrite complex of SR(Fe(II)) as the final product. This finding is clearly supported by laser flash photolysis studies on the SR/NO reaction mixture, which do not reveal simple NO photolabilization from SR(Fe(III))(NO), but rather involve the generation of at least three photoinduced intermediates decaying with different rate constants to the starting material. The species formed along the proposed reaction pathways were characterized by FTIR and EPR spectroscopy. The results are discussed in terms of their relevance for the biological function of cytochrome P450 enzymes and in context of results for the reaction of NO with imidazole- and thiolate-ligated iron(III) hemoproteins.     

Mechanistic information on the reversible binding of NO to selected iron(II) chelates from activation parameters

Mechanistic insight on the reversible binding of NO to Fe(II) chelate complexes as potential catalysts for the removal of NO from effluent gas streams has been obtained from the temperature and pressure parameters for the "on" and "off" reactions determined using a combination of flash photolysis and stopped-flow techniques. These parameters are correlated with those for water exchange reactions on the corresponding Fe(II) and Fe(III) chelate complexes, from which mechanistic conclusions are drawn. Small and positive Delta V(++) values are found for NO binding to and release from all the selected complexes, consistent with a dissociative interchange (I(d)) mechanism. The only exception in the series of studied complexes is the binding of NO to [Fe(II)(nta)(H(2)O)(2)](-). The negative volume of activation observed for this reaction supports the operation of an I(a) ligand substitution mechanism. The apparent mechanistic differences can be accounted for in terms of the electronic and structural features of the studied complexes. The results indicate that the aminocarboxylate chelates affect the rate and overall equilibrium constants, as well as the nature of the substitution mechanism by which NO coordinates to the selected complexes. There is, however, no simple correlation between the rate and activation parameters and the selected donor groups or overall charge on the iron(II) complexes.