H-1 and F-19 NMR relaxation time studies in (NH4)(2)ZrF6 superionic conductor

H-1 and F-19 spin-lattice relaxation times in polycrystalline diammonium hexafluorozirconate have been measured in the temperature range of 10-400 K to elucidate the molecular motion of both cation and anion. Interesting features such as translational diffusion at higher temperatures, molecular reorientational motion of both cation and anion groups at intermediate temperatures and quantum rotational tunneling of the ammonium group at lower temperatures have been observed. Nuclear magnetic resonance (NMR) relaxation time results correlate well with the NMR second moment and conductivity studies reported earlier.

Relationship between annual rainfall and tree mortality in a tropical dry forest: Results of a 19-year study at Mudumalai, southern India

Variability in rainfall is known to be a major influence on the dynamics of tropical forests, especially rates and patterns of tree mortality. In tropical dry forests a number of contributing factors to tree mortality, including dry season fire and herbivory by large herbivorous mammals, could be related to rainfall patterns, while loss of water potential in trees during the dry season or a wet season drought could also result in enhanced rates of death. While tree mortality as influenced by severe drought has been examined in tropical wet forests there is insufficient understanding of this process in tropical dry forests. We examined these causal factors in relation to inter-annual differences in rainfall in causing tree mortality within a 50-ha Forest Dynamics Plot located in the tropical dry deciduous forests of Mudumalai, southern India, that has been monitored annually since 1988. Over a 19-year period (1988-2007) mean annual mortality rate of all stems >1 cm dbh was 6.9 +/- 4.6% (range = 1.5-17.5%); mortality rates broadly declined from the smaller to the larger size classes with the rates in stems >30 cm dbh being among the lowest recorded in tropical forest globally. Fire was the main agent of mortality in stems 1-5 cm dbh, elephant-herbivory in stems 5-10 cm dbh, and other natural causes in stems > 10 cm dbh. Elephant-related mortality did not show any relationship to rainfall. On the other hand, fire-related mortality was significantly negatively correlated to quantity of rainfall during the preceding year. Mortality due to other causes in the larger stem sizes was significantly negatively correlated to rainfall with a 2-3-year lag, suggesting that water deficit from mild or prolonged drought enhanced the risk of death but only with a time lag that was greater than similar lags in tree mortality observed in other forest types. In this respect, tropical dry forests growing in regions of high rainfall variability may have evolved greater resistance to rainfall deficit as compared to tropical moist or temperate forests but are still vulnerable to drought-related mortality.

Silva Fennica Vol. 19, 1985.

Julkaistu Silva Fennica Vol. 19(4) -numeron liitteenä.

Role of neutral metabolites in microbial conversion of 3beta-acetoxy-19-hydroxycholest-5-ene into estrone

Biotransformation of 3 beta-acetoxy-19-hydroxycholest-5-ene (19-HCA, 6 g) by Moraxella sp. was studied. Estrone (712 mg) was the major metabolite formed. Minor metabolites identified were 5 alpha-androst-1-en-19-ol-3,17-dione (33 mg), androst-4-en-19-ol-3,17-dione (58 mg), androst-4-en-9 alpha,19-diol-3,17-dione (12 mg), and androstan-19-ol-3,17-dione (1 mg). Acidic metabolites were not formed. Time course experiments on the fermentation of 19-HCA indicated that androst-4-en-19-ol-3,17-dione was the major metabolite formed during the early stages of incubation. However with continuing fermentation its level dropped, with a concomitant increase in estrone. Fermentation of 19-HCA in the presence of specific inhibitors or performing the fermentation for a shorter period (48 h) did not result in the formation of acidic metabolites. Resting-cell experiments carried out with 19-HCA (200 mg) in the presence of alpha,alpha'-bipyridyl led to the isolation of three additional metabolites, viz., cholestan-19-ol-3-one (2 mg), cholest-4-en-19-ol-3-one (10 mg), and cholest-5-en-3 beta,19-diol (12 mg). Similar results were also obtained when n-propanol was used instead of alpha,alpha'-bipyridyl. Resting cells grown on 19-HCA readily converted both 5 alpha-androst-1-en-19-ol-3,17-dione and androst-4-en-19-ol-3,17-dione into estrone. Partially purified 1,2-dehydrogenase from steroid-induced Moraxella cells transformed androst-4-en-19-ol-3,17-dione into estrone and formaldehyde in the presence of phenazine methosulfate, an artificial electron acceptor. These results suggest that the degradation of the hydrocarbon side chain of 19-HCA does not proceed via C-22 phenolic acid intermediates and complete removal of the C-17 side chain takes place prior to the aromatization of the A ring in estrone. The mode of degradation of the sterol side chain appears to be through the fission of the C-17-C-20 bond. On the basis of these observations, a new pathway for the formation of estrone from 19-HCA in Moraxella sp. has been proposed.

Structure of 9[alpha],19-dihydroxy-4-androstene-3,17-dione

C19H26O4, M(r) = 318.41, orthorhombic, P2(1)2(1)2(1), a = 10.591 (1), b = 11.133 (1), c = 13.657 (2) angstrom, V = 1610.29 angstrom 3, Z = 4, D(m) (flotation in KI) = 1.301, D(x) = 1.313 g cm-3, Mo K-alpha, lambda = 0.7107 angstrom, mu = 0.85 cm-1, F(000) = 688, T = 293 K, R = 0.057 for 1253 significant reflections. The A ring is disordered with atoms C(2) and O(19) occupying two possible sites. The molecules are held together by a hydrogen bond [O(9)...O(17) = 2.89 angstrom].

Structure of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecyl 1,10-ditosylate by X-ray crystallography and F-19-NMR spectroscopy

2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecyl 1,10-ditosylate and its precursors were synthesized and characterized by H-1- and F-19-NMR spectroscopic methods and X-ray crystallography. These compounds are building blocks for the syntheses of the surfactants containing polyperfluoromethylene spacer. The molecule has extended all-trans conformation with molecular symmetry (1) over bar (C-i). There is a reasonably strong C-H ... O interaction in the crystal and there are two F ... F intermolecular contact distances less than the sum of van der Waals radii. (C) 1999 Elsevier Science B.V. All rights reserved.

The interaction of N-trifluoroacetylgalactosamine and its derivatives with winged bean (Psophocarpus tetragonolobus) basic agglutinin reveals differential mechanism of their recognition: a fluorine-19 nuclear magnetic resonance study

Here, we show the binding results of a leguminosae lectin, winged bean basic agglutinin (WBA I) to N-trifluoroacetylgalactosamine (NTFAGalN), methyl-alpha-N-trifluoroacetylgalactosamine (Me alpha NTFAGalN) and methyl-beta-tifluoroacetylgalactosamine (Me beta NTFAGalN) using (19) F NMR spectroscopy. No chemical shift difference between the free and bound states for NTFAGalN and Me beta NTFAGalN, and 0.01-ppm chemical shift change for Me alpha NTFAGalN, demonstrate that the Me alpha NTFAGalN has a sufficiently long residence time on the protein binding site as compared to Me beta NTFAGalN and the free anomers of NTFAGalN. The sugar anomers were found in slow exchange with the binding site of agglutinin. Consequently, we obtained their binding parameters to the protein using line shape analyses. Aforementioned analyses of the activation parameters for the interactions of these saccharides indicate that the binding of alpha and beta anomers of NTFAGalN and Me alpha NTFAGalN is controlled enthalpically, while that of Me beta NTFAGalN is controlled entropically. This asserts the sterically constrained nature of the interaction of the Me beta NTFAGalN with WBA I. These studies thus highlight a significant role of the conformation of the monosaccharide ligands for their recognition by WBA I.

Quick measurement of H-1-F-19 scalar couplings from the complex NMR spectra by real-time spin edition

Most often the measurement of VHF from the conventional 1D H-1 NMR spectrum is severely hindered consequent to similar magnitudes of JHF and JHH couplings and the spectral multiplicity pattern. The present study reports a new 1D NMR technique based on real time spin edition, which removes all JHF and JHH while retaining only VHF of a chosen fluorine. The obtained spectrum is significantly simplified and permits straightforward determination of all possible VHF values of a chosen fluorine. Due to one dimensional nature, the method is much faster compared to 2D GET-SERF by 1-2 orders of magnitude. (C) 2015 Elsevier B.V. All rights reserved.

La ley moral natural y ley positiva humana en el opúsculo “La filosofía jurídica del artículo 19 de la Constitución Nacional”, de Arturo Enrique Sampay

La Constitución Nacional reconoce un orden de conducta instituido por Dios y otro instituido por el Estado… el débito legal debe resultar conforme al débito moral. Si así no fuera, cualquier imposición del legislador no sería derecho sino un acto de violencia desnaturalizando el poder que el Estado tiene de reforzar con débito eventualmente coercible obligaciones emergentes de la virtud de la justicia. En este trabajo nos ocuparemos de la relación entre ley moral natural y la ley positiva humana a partir de las consideraciones que Arturo Enrique Sampay2 formula en su obra, La filosofía jurídica del Artículo 19 de la Constitución Nacional3. Sampay desarrolla el tópico principalmente con la inspiración de la doctrina de Tomás de Aquino.

Sapientia, 1951, Vol. VI, nº 19 (número completo)

Contenido: Filosofía y originalidad / La Dirección – La idea de posible y el sentido de la existencia : génesis de esta idea / André Marc – Carácter existencial de la demostración de la existencia de Dios / Octavio N. Derisi – La naturaleza en la ciencia físico-matemática / Raimundo Paniker – Razones seminales y formas substanciales : agustinismo y tomismo / F. J. Thonnard – Notas y comentarios -- Bibliografía

Prudentia Iuris, 1988, n° 19-20 (número completo)

Contenido: Editorial – Cum o Vrea Domnul. “Como Dios quiera” : ¿cómo entiende el rumano la sumisión a la voluntad de Dios? / Ioan Dan – Algunas cuestiones éticas y penales de las modernas técnicas biomédicas / Guillermo Jorge Yacobucci – El racionalismo moderno : configuración y proyecciones / Bernardino Bravo Lira – El pensamiento político en orígenes de Alejandría / Néstor Daniel Villa – El proceso penal de menores / Miguel Ángel Madariaga – Documentos -- Recensiones