Water has two nuclear-spin isomers: ortho- and para-H2O. Some observations of interstellar space and cometary comae have reported the existence of gaseous H2O molecules with anomalous ortho-to-para ratios (OPRs) less than the statistical value of three. This has been often used to estimate the formation temperature of ice on dust, which is inferred to be below 50 K. The relation between the nuclear-spin dynamics of H2O in ice at low temperatures and the OPR of gaseous H2O desorbed from the ice has yet to be explored in a laboratory. Consequently, the true meaning of the observed OPRs remains debated. We measure the OPR of H2O photodesorbed from ice made from para-H2O monomers at 11 K, which was prepared by the sublimation of Ne from a para-H2O/Ne matrix. The photodesorbed H2O molecules from the ice have the statistical OPR value of three, demonstrating the immediate nuclear-spin-state mixing of H2O toward the statistical value of ice even at 11 K. The OPR of H2O thermally desorbed from the ice also shows the expected statistical value. Our results indicate that the OPR of H2O desorbed from interstellar ice should be the statistical value regardless of the formation process of the ice, which cannot be used to deduce the ice-formation temperature. This study highlights the importance of interstellar gas-phase processes in understanding anomalous abundance ratios of nuclear-spin isomers of molecules in space.
fotonovela del mono mario 46
El proyecto de instrumentación de mayor importancia que ha tenido el Instituto de Astrofisica de Canarias en los últimos afios ha sido el diseflo y construcción del te1escopio IAC8O. Este requería del esfuerzo con junto en mecnica, óptica y electrónica, lo que facilitó la estructuración y el crecimiento de los respectivos grupos de trabajo, que posteriormente se integraron en departamentos En su origen (1977), el telescopio IAC80 fue concebido como un sistema clásico tipo Cassegrain, con una razón focal F/i 1.3 para el sistema Casse grain y una razón focal F/20 para el sistema Coudé. Posteriormente, aunque se mantuvo la filosofia de que el sistema básico fuera el F/11.3, se consideró conveniente el diseño de secundarios para razones focales F/16 y F/32, y se eliminó el de F/20. Sin embargo, dada la importancia relativa que un foco estrictamente fotográfico tiene en un telescopio moderno, diseñado básicamente para fotometría fotoeléctrica y con un campo util mínimamente de 40 minutos de arco, se decídió Ilevar a cabo el diseño de un secundario F/8 con un sistema corrector de campo, pero que estuviera formado únicamente por lentes con superficies esféricas para que asl su construcción fuera posible en España ó en México. La creciente utilización de detectores bidimensionales para fines de investigación astron6mica y la viabilidad de que en un futuro cercano éstos tengan un área sensible cada vez mayor, hicieron atractiva la idea de tener diseñado un sistema corrector de campo para el foco primario (F/3), con un campo útil mínimo de un grado, y también con la limitante de que sus componentes tuvieron sólamente supérficies esféricas. Ambos diseños de los sis-temas correctores de campo se llevaron a cabo, en gran medida, como parte de un proyecto de colaboración e intercambio en el área de diseño y evaluación de sistemas ópticos.
El telescopio UNAM2l2 fue inaugurado hace siete años y concebido para trabajar en las razones focales: f/7.5, F/13.5, F/27 y F/98. El diseño Ritchey-Chretién corresponde a la razón focal F/7.5 y el foco primario (F/2.286) no se consideró como utilizable para fotografía directa. En el Instituto de Astronomía de la UNAM, se diseñó y construyó un sistema corrector de campo para la razón focal F/7.5, que actualmente está en funcionamiento. Dentro de un programa de colaboración en diseflo y evaluación de sistemas ópticos, entre el Instituto de Astrofísica de Canarias y el Instituto de Astronomía de la UNAM, decidimos intentar el diseño de una correctora de campo para el foco primario del tȩlescopio UNAM212 bajo la consideración de que no son insalvables los problemas que implicaría su instalación y de que es muy posible que, en un futuro relativamente cercano, podamom tener un detector bidimenmional tipo Mepsicrón cuya área sensible haga tentadora la idea de construir la cámara directa para foco primario
The relationship between the structure and activity of meta- and para-hydroxylated monophenols was studied during their tyrosinase-catalysed hydroxylation and the rate-limiting steps of the reaction mechanism were identified. The para-hydroxylated substrates permit us to study the effect of a substituent (R) in the carbon-1 position (C-1) of the benzene ring on the nucleophilic attack step, while the meta group permits a similar study of the effect on the electrophilic attack step. Substrates with a -OCH3 group on C-1, as p-hydroxyanisol (4HA) and m-hydroxyanisol (3HA), or with a -CH2OH group, as p-hydroxybenzylalcohol (4HBA) and m-hydroxybenzylalcohol (3HBA), were used because the effect of the substituent (R) size was assumed to be similar. However, the electron-donating effect of the -OCH3 group means that the carbon-4 position (C-4) is favoured for nucleophilic attack (para-hydroxylated substrates) or for electrophilic attack (meta-hydroxylated substrates). The electron-attracting effect of the -CH2OH group has the opposite effect, hindering nucleophilic (para) or electrophilic (meta) attack of C-4. The experimental data point to differences between the maximum steady-state rate (V(M)Max) of the different substrates, the value of this parameter depends on the nucleophilic and electrophilic attack. However, differences are greatest in the Michaelis constants (K(M)m), with the meta-hydroxylated substrates having very large values. The catalytic efficiency k(M)cat/K(M)m is much greater for thepara-hydroxylated substrates although it varies greatly between one substrate and the other. However, it varies much less in the meta-hydroxylated substrates since this parameter describes the power of the nucleophilic attack, which is weaker in the meta OH. The large increase in the K(M)m of the meta-hydroxylated substrates might suggest that the phenolic OH takes part in substrate binding. Since this is a weaker nucleophil than the para-hydroxylated substrates, the binding
Human autoimmune diseases are caused by a variety of factors, such as environmental chemicals, including para-nonylphenol. Macrophages play many critical roles in the regulation of immunity and the progression of autoimmune diseases. However, little information is available regarding the effects of para-nonylphenol on cellular signaling pathways and the death of these cells in vitro. Here, we show that very high concentrations of para-nonylphenol (50-100 μM) induce apoptosis in U937 human monocyte leukemia cells in a dose-dependent manner. Cell viability was judged using the trypan blue exclusion method. FACS analysis for DNA fragmentation was conducted, cellular signaling pathways were evaluated using western blot analysis, and caspase activity was measured by using substrates. U937 cells were differentiated by PMA. Treatment with > 50 μM para-nonylphenol induced apoptosis in U937 monocyte cells and MCF- 7 and MDA-MB231 human breast cancer cells. We found cytochrome c release from the mitochondria to the cytoplasm, DNA fragmentation, and decreased expression of anti-apoptotic protein Bcl-XL. Caspase 3 and 9 were induced, but caspase 1 and 3-inhibitor treatment suppressed apoptosis. Para-nonylphenol decreased the levels of activated AKT and increased the levels of activated JNK/SAPK at 15 min after treatment. Furthermore, with PMA treatment, U937 cells were differentiated into a macrophage-like phenotype and showed attenuated cell death against para-nonylphenol. As this assay system is simple and rapid, it may represent a useful artificial tool to clarify the signaling pathways of apoptotic cell death in human monocytes in vitro. Copyright Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.
Rate constants were measured for the oxidative chlorodehydrogenation of (R,S)-2-phenoxypropanoic acid and nine ortho-, ten para- and five meta-substituted derivatives using (R,S)-1-chloro-3-methyl-2,6-diphenylpiperidin-4-one (NCP) as chlorinating agent. The kinetics was run in 50% (v/v) aqueous acetic acid acidified with perchloric acid under pseudo-first-order conditions with respect to NCP at temperature intervals of 5 K between 298 and 318 K, except at the highest temperature for the meta derivatives. The dependence of rate constants on temperature was analyzed in terms of the isokinetic relationship (IKR). For the 20 reactions studied at five different temperatures, the isokinetic temperature was estimated to be 382 K, which suggests the preferential involvement of water molecules in the rate-determining step. The dependence of rate constants on meta and para substitution was analyzed using the tetralinear extension of the Hammett equation. The parameter lambda for the para/meta ratio of polar substituent effects was estimated to be 0.926, and its electrostatic modeling suggests the formation of an activated complex bearing an electric charge near the oxygen atom belonging to the phenoxy group. A new approach is introduced for examining the effect of ortho substituents on reaction rates. Using IKR-determined values of activation enthalpies for a set of nine pairs of substrates with a given substituent, a linear correlation is found between activation enthalpies of ortho and para derivatives. The correlation is interpreted in terms of the selectivity of the reactant toward para- or ortho-monosubstituted substrates, the slope of which being related to the ortho effect. This slope is thought to be approximated by the ratio of polar substituent effects from ortho and para positions in benzene derivatives. Using the electrostatic theory of through-space interactions and a dipole length of 0.153 nm, this ratio was calculated at various positions of a charged reaction 2ff7e9595c
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