Descripción: Crystal structures are presented for two members of the homologous series of 1,2-dibromo-4,5-dialkoxybenzenes, viz. those with decyloxy and hexadecyloxy substituents, namely 1,2-dibromo-4,5-bis(decyloxy)benzene, C26H44Br2O2, (II), and 1,2-dibromo-4,5-bis(hexadecyloxy)benzene, C38H68Br2O2, (III). The relative influences which halogen bonding, π- π stacking and van der Waals interactions have on these structures are analysed and the results compared with those already found for the lightest homologue, 1,2-dibromo-4,5- dimethoxybenzene, (I) [Cukiernik, Zelcer, Garland & Baggio (2008). Acta Cryst. C64, o604-o608]. The results confirm that the prevalent interactions stabilizing the structures of (II) and (III) are van der Waals contacts between the aliphatic chains. In the case of (II), weak halogen C - Br ⋯(Br - C) ′ interactions are also present and contribute to the stability of the structure. In the case of (III), van der Waals interactions between the aliphatic chains are almost exclusive, weaker C - Br ⋯ π interactions being the only additional interactions detected. The results are in line with commonly accepted models concerning trends in crystal stability along a homologous series (as measured by their melting points), but the earlier report for n = 1, and the present report for n = 10 and 16, are among the few providing single-crystal information validating the hypothesis.

Descripción: The title compound, C4H6N2S3, has two very similar molecules per asymmetric unit. The nine non-H atoms in each molecule are coplanar, both having comparable r.m.s. deviations of 0.002 Å. The main interest in the rather simple structure resides in a survey of very weak (in some cases, borderline) non-bonding interactions of various kinds, viz. S···S, C - H·π, π-π [centroid-centroid distance = 3.8958 (13) Å] and C - S- ···π [3.7271 (11) Å], which act as the major driving force for the arrangement of molecules in the structure. The role of long, though highly directional, S···S contacts (d > 3.60 Å), and their relevance to the stability of the structure is discussed.

Descripción: In daily life, memories are intertwined events. Little is known about the mechanisms involved in their interactions. Using two hippocampus-dependent (spatial object recognition and contextual fear conditioning) and one hippocampus-independent (conditioned taste aversion) learning tasks, we show that in rats subjected to weak training protocols that induce solely short term memory (STM), long term memory (LTM) is promoted and formed only if training sessions took place in contingence with a novel, but not familiar, experience occurring during a critical time window around training. This process requires newly synthesized proteins induced by novelty and reveals a general mechanism of LTM formation that begins with the setting of a "learning tag" established by a weak training. These findings represent the first comprehensive set of evidences indicating the existence of a behavioral tagging process that in analogy to the synaptic tagging and capture process, need the creation of a transient, protein synthesis-independent, and input specific tag.

Descripción: Pineal hormone melatonin (N-acetyl-5-methoxytryptamine) is thought to modulate the calcium/calmodulin signaling pathway either by changing intracellular Ca2+ concentration via activation of its G-protein-coupled membrane receptors, or through a direct interaction with calmodulin (CaM). The present work studies the direct interaction of melatonin with intact calcium-saturated CaM both experimentally, by fluorescence and nuclear magnetic resonance spectroscopies, and theoretically, by molecular dynamics simulations. The analysis of the experimental data shows that the interaction is calcium-dependent. The affinity, as obtained from monitoring 15N and 1H chemical shift changes for a melatonin titration, is weak (in the millimolar range) and comparable for the N- and C-terminal domains. Partial replacement of diamagnetic Ca2+ by paramagnetic Tb3+ allowed the measurement of interdomain NMR pseudocontact shifts and residual dipolar couplings, indicating that each domain movement in the complex is not correlated with the other one. Molecular dynamics simulations allow us to follow the dynamics of melatonin in the binding pocket of CaM. Overall, this study provides an example of how a combination of experimental and theoretical approaches can shed light on a weakly interacting system of biological and pharmacological significance.

Descripción: The molecular structure of the title compound, [Zn(CH3COO) 2(C12H12N2)], consists of isolated molecules bisected by a twofold rotation axis which goes through the ZnII cation and halves the organic base through the central C-C bond. The Zn II ion is coordinated by two N atoms from one molecule of the aromatic base and four O atoms from two bidentate, symmetry-related acetate anions, which coordinate asymmetrically [Zn-O distances of 2.058(2) and 2.362(3)Å], while the two Zn-N bond distances are equal as imposed by symmetry [2.079(2)Å]. The crystal structure is supported by a number of weak C-H⋯O interactions and C-H⋯π contacts, with no π-π interactions present, mainly hindered by the substituent methyl groups and the relative molecular orientation. The result is a three-dimensional structure in which each molecule is linked to eight different neighbors.

Descripción: The expanded bow shock on and around "the day the solar wind almost disappeared" (11 May 1999) allowed the Geotail spacecraft to make a practically uninterrupted 54-h-long magnetosheath pass near dusk (16:30-21:11 magnetic local time) at a radial distance of 24 to 30 RE (Earth radii). During most of this period, interplanetary parameters varied gradually and in such a way as to give rise to two extreme magnetosheath structures, one dominated by magnetohydrodynamic (MHD) effects and the other by gas dynamic effects. We focus attention on unusual features of electromagnetic ion wave activity in the former magnetosheath state, and compare these features with those in the latter. Magnetic fluctuations in the gas dynamic magnetosheath were dominated by compressional mirror mode waves, and left-and right-hand polarized electromagnetic ion cyclotron (EIC) waves transverse to the background field. In contrast, the MHD magnetosheath, lasting for over one day, was devoid of mirror oscillations and permeated instead by EIC waves of weak intensity. The weak wave intensity is related to the prevailing low solar wind dynamic pressures. Left-hand polarized EIC waves were replaced by bursts of right-hand polarized waves, which remained for many hours the only ion wave activity present. This activity occurred when the magnetosheath proton temperature anisotropy (=Tp, ⊥/Tp, ∥-1) became negative. This was because the weakened bow shock exposed the magnetosheath directly to the (negative) temperature anisotropy of the solar wind. Unlike the normal case studied in the literature, these right-hand waves were not by-products of left-hand polarized waves but derived their energy source directly from the magnetosheath temperature anisotropy. Brief entries into the low latitude boundary layer (LLBL) and duskside magnetosphere occurred under such inflated conditions that the magnetospheric magnetic pressure was insufficient to maintain pressure balance. In these crossings, the inner edge of the LLBL was flowing sunward. The study extends our knowledge of magnetosheath ion wave properties to the very low solar wind dynamic pressure regime. © European Geosciences Union 2005.

Descripción: Longitudinal dependences of stratospheric gravity wave (GW) fluctuations and lower ionospheric irregularities (sporadic E) at midlatitudes are studied by means of radio occultation data of the Global Positioning System/Meteorology Experiment (GPS/MET) satellite mission. The zonal average of temperature variance of GW fluctuations with vertical scales less than 7 km at northern midlatitudes is observed to be similar to that at southern midlatitudes, but there is a significant interhemispheric difference in the longitudinal dependence of GW fluctuations. The GPS/MET data at northern midlatitudes show a rapid change of the gravity wave distribution from 25 to 35 km height, resulting in a broad maximum of temperature variance located over the Atlantic and Eurasia. We only find in the wave distribution at h = 25 km some weak traces of possible orographic effects. On the other hand, the distribution of GW fluctuations at southern midlatitudes has a strong and sharp maximum over Andes, which is obviously due to orographic wave generation by the interaction of surface wind with the Andean mountain ridge. This observation of the new GPS radio occultation technique is in agreement with previous measurements of spaceborne microwave and infrared limb sounders. The amplitude of the average wave field increases with height over Andes, while the amplitude maximum moves westward, against the prevailing wind. The temperature fluctuations have an apparent, dominant vertical wavelength of around 6 km. In situ measurements by a balloon-borne rawinsonde at Ushuaia, Argentina (54.7°S, 68.1°W) are compared to a simultaneous GPS/MET temperature profile. The balloon observations of temperature and horizontal wind are interpreted by a large amplitude mountain wave propagating to the upper stratosphere. Wave characteristics and atmospheric background conditions are investigated in detail for this mountain wave observation. Finally, the GPS/MET experiment indicates enhanced sporadic E in the lower ionosphere over Southern Andes. We assume that these plasma irregularities are generated by enhanced, upward wave flux due to the possible orographic effect of Andes. Copyright 2002 by the American Geophysical Union.