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Reverse Process (reverse + process)
Selected AbstractsA ,3 -Alkoxo-Bridged Tetranuclear [Cu4L2] Copper(II) Complex of a Hexadentate N2O4 Donor Ligand with a [6 + 0] Cu4O4 Cubane Core: Synthesis, Crystal Structure, and Magnetic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2010Dipankar Maity Abstract A novel hexacoordinating non-Schiff base ligand (H4L) with N2O4 donor atoms has been synthesized by simple Mannich reactions. The use of this ligand with Cu(ClO4)2·6H2O in different molar ratios as well as pH leads to the formation of a mononuclear species and a tetranuclear CuII complex possessing a cubane [Cu4L2] core with almost equal Cu···Cu separation. In the presence of an excess amount of copper(II) ions and triethylamine at reflux, the mononuclear [CuH2L] species can be converted into the tetranuclear one, whereas the reverse process was not observed even after prolonged reaction time. Both the complexes have been characterized by single-crystal X-ray diffraction and magnetic measurements. Magnetic studies reveal that complex 1 displays a paramagnetic Curie-type behavior whereas 2 displays a singlet-spin ground state induced by strong intramolecular antiferromagnetic interactions. [source] Rate constants for H + CH4, CH3 + H2, and CH4 dissociation at high temperatureINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 11 2001J. W. Sutherland The Laser Photolysis-Shock Tube technique coupled with H-atom atomic resonance absorption spectrometry has been used to study the reaction, H + CH4 , CH3 + H2, over the temperature range, 928,1697 K. Shock-tube studies on the reverse of this reaction, CH3 + H2 , H + CH4, using CH3I dissociation in the presence of H2 yielded H-atom formation rates and rate constants for the reverse process over the temperature range, 1269,1806 K. These results were transformed (using well-established equilibrium constants) to the forward direction. The combined results for H + CH4 can be represented by an experimental three parameter expression, k = 6.78 × 10,21 T3.156 exp(,4406 K/T) cm3 molecule,1 s,1 (348,1950 K) that was evaluated from the present work and seven previous studies. Using this evaluation, disagreements between previously reported values for the dissociation of CH4 could be reconciled. The thermal decomposition of CH4 was then studied in Kr bath gas. The dissociation results agreed with the earlier studies and were theoretically modeled with the Troe formalism. The energy transfer parameter necessary to explain both the present results and those of Kiefer and Kumaran (J Phys Chem 1993, 97, 414) is, ,,,E,all/cm,1 = 0.3323 T0.7. The low temperature data on the reverse reaction, H + CH3 (in He) from Brouard et al. (J Phys Chem 1989, 93, 4047) were also modeled with the Troe formalism. Lastly, the rate constant for H + CH4 was theoretically calculated using conventional transition state theory with Eckart tunneling corrections. The potential energy surface used was from Kraka et al. (J Chem Phys 1993, 99, 5306) and the derived T-dependence with this method agreed almost perfectly with the experimental evaluation. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 669,684, 2001 [source] Quantification of glycerol diffusion in human normal and cancer breast tissues in vitro with optical coherence tomographyLASER PHYSICS LETTERS, Issue 4 2010H.Q. Zhong Abstract Optical coherence tomography (OCT) holds great promise as a routine research tool for analysis of identifying the boundaries between normal and diseased breast tissue in vitro and in vivo. However, despite the depth penetration afforded by this imaging modality, light attenuation in tissues imposes limitations. Here we studied the optical clearing effect of glycerol in human cancer and normal breast tissues with OCT for functional imaging to monitor. Depth- and time-resolved profiles for OCT signal enhancement were presented. The results show that the OCT imaging depth and imaging contrast of breast tissues have been improved after application of 60% glycerol in the 2-D OCT images. The OCT slope signals of breast tissues decreased as glycerol diffusion into tissues, therefore, the water and intercellular fluids were drawn out from tissues. Then the reverse process due to water was drawn back into the cells as a result of its affinity for water. The permeability coefficient of 60% glycerol was (3.14 ± 0.07) × 10,5 cm/s in breast cancer tissues, and (0.89 ± 0.02) × 10,5 cm/s in normal breast tissues, respectively. The permeability coefficient of glycerol in cancer tissues was 3.54-fold than that in normal tissues. These results demonstrate that the optical clearing of normal and cancer breast tissues are improved after application of glycerol. (© 2010 by Astro Ltd., Published exclusively by WILEY-VCH Verlag GmbH & Co. KGaA) [source] A new approach to automated first-order multiplet analysisMAGNETIC RESONANCE IN CHEMISTRY, Issue 5 2002Sergey Golotvin Abstract The dependence of the values of NMR spin,spin coupling constants on molecular conformation can be a valuable tool in the structure determination process. The continuing increase in the resonance frequency of modern NMR spectrometers allows an increasing number of resonances to be examined using first-order multiplet analysis. While this can easily be done for the simplest patterns (doublets, triplets, quartets), more complex patterns can be extremely difficult to analyze. The task of deducing the coupling constant values from a multiplet is the reverse process of generating a conventional splitting tree from a single line (chemical shift) by sequential branching using a given set of coupling constants. We present a simple, straightforward method of deducing coupling constant values from first-order multiplets based on a general inverted splitting tree algorithm but also including a peak intensity normalization procedure that utilizes multiplet symmetry and generates a set of possible first-order intensity distribution patterns. When combined with an inverted splitting tree algorithm, it is possible to find an intensity pattern that allows the deduction of a proper set of coupling constants. Copyright © 2002 John Wiley & Sons, Ltd. [source] Crossing Borders: Globalization as Myth and Charter in American Transnational Consumer MarketingAMERICAN ETHNOLOGIST, Issue 2 2000Kalman Applbaum In this article, I explore the strategic practices and cultural theories of marketing managers in three U.S.-based transnational corporations (TNCs) as seek to meaningfully direct their products across national borders. While cultural anthropologists have lately focused on local adaptation and appropriation of TNCs' products to local meanings, the reverse process by which TNCs co-opt local meanings to a universalizing evolutionary paradigm,in what they have come to regard as a consumption-led new global order,has not been examined. Globalization is explored as a key cultural concept driving marketing managers' practices,the myth and charter behind large TNC border crossings. [consumer marketing, globalization, transnational corporations, United States] [source] Protein dynamics control proton transfer from bulk solvent to protein interior: A case study with a green fluorescent proteinPROTEIN SCIENCE, Issue 7 2005Anoop M. Saxena Abstract The kinetics of proton transfer in Green Fluorescent Protein (GFP) have been studied as a model system for characterizing the correlation between dynamics and function of proteins in general. The kinetics in EGFP (a variant of GFP) were monitored by using a laser-induced pH jump method. The pH was jumped from 8 to 5 by nanosecond flash photolysis of the "caged proton," o -nitrobenzaldehyde, and subsequent proton transfer was monitored by following the decrease in fluorescence intensity. The modulation of proton transfer kinetics by external perturbants such as viscosity, pH, and subdenaturing concentrations of GdnHCl as well as of salts was studied. The rate of proton transfer was inversely proportional to solvent viscosity, suggesting that the rate-limiting step is the transfer of protons through the protein matrix. The rate is accelerated at lower pH values, and measurements of the fluorescence properties of tryptophan 57 suggest that the enhancement in rate is associated with an enhancement in protein dynamics. The rate of proton transfer is nearly independent of temperature, unlike the rate of the reverse process. When the stability of the protein was either decreased or increased by the addition of co-solutes, including the salts KCl, KNO3, and K2SO4, a significant decrease in the rate of proton transfer was observed in all cases. The lack of correlation between the rate of proton transfer and the stability of the protein suggests that the structure is tuned to ensure maximum efficiency of the dynamics that control the proton transfer function of the protein. [source] Effect of impeller clearance on liquid flow within an unbaffled vessel agitated with a forward,reverse rotating impellerTHE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, Issue 6 2009Masanori Yoshida Abstract For an unbaffled agitated vessel with an unsteadily forward,reverse rotating impeller whose rotation proceeds with repeated acceleration, deceleration, and stop,reverse processes, liquid flow was studied through visualisation and measurement using particle tracking velocimetry (PTV). A disk turbine impeller with six flat blades was used with varied height settings. The impeller clearance and its forward,reverse rotation cycle characterised the impeller region flow: the radially outward flow in the deceleration process for the larger clearance relative to the vessel diameter of 1/3, and the axially downward flow in the acceleration process for the smaller clearance relative to the vessel diameter of 1/8. The flow patterns within the vessel resulting from the impeller's larger and smaller clearances were outlined, respectively, by double loops and a single loop of circulation, resembling the pattern produced by unidirectionally rotating turbine-type impellers. The discharge flow was revealed to contain a comparable level of periodic circumferential velocity component, irrespective of the impeller clearance. On a étudié l'écoulement liquide par visualisation et mesure en utilisant la vélocimétrie avec poursuite de trajectoire pour une cuve non compartimentée et agitée avec un agitateur rotatif avant-arrière non stable dont la rotation est composée de périodes répétées d'accélération, de ralentissement et d'arrêt-marche arrière. Un agitateur à six pales plates a été utilisé avec quatre réglages de hauteur différents. Le dégagement de l'agitateur et son cycle de rotation avant-arrière caractérisaient l'écoulement liquide dans la région de l'agitateur : l'écoulement radial vers l'extérieur dans le processus de décélération pour le dégagement le plus important par rapport au diamètre de la cuve de 1/3 et l'écoulement axial vers le bas dans le processus d'accélération pour le dégagement le plus petit par rapport au diamètre de la cuve de 1/8. Les modèles d'écoulement intérieurs de la cuve résultant du plus grand et du plus petit dégagements de l'agitateur ont été décrits, respectivement, par des doubles boucles et une simple boucle de circulation, ce qui ressemble au modèle produit par des agitateurs à hélice unidirectionnels. On a révélé que l'écoulement de sortie contenait un niveau comparable de vélocité périodique périphérique, indépendamment du dégagement de l'agitateur. [source] | ||||||||||