First donor-acceptor interaction promoted gelation of organic fluids

In recent years there has been considerable interest in developing new types of gelators of organic solvents.1 Despite the recent advances, a priori design of a gelator for gelling a given solvent has remained a challenging task. Various noncovalent interactions like hydrogen-bonding,2 metal coordination3 etc. have been used as the driving force for the gelation process. A special class of cholesterol-based gelators were reported by Weiss,4 and by Shinkai.5 Gels derived from these molecules have been used for chiral recognition/sensing,6 for studying photo- and metal-responsive functions,7 and as templates to make hollow fiber silica.8 Other types of organogels have been used for designing polymerized 9 and reverse aerogels,10 and in molecular imprinting.11 Hanabusa’s group has recently reported organogels with a bile acid derivative.12 This has prompted us to disclose our results on a novel electron donor–acceptor (EDA) interaction mediated two-component13 gelator system based on the bile acid14 backbone.

Molecular theory for the effects of specific solute-solvent interaction on the diffusion of a solute particle in a molecular liquid

An understanding of the effect of specific solute-solvent interactions on the diffusion of a solute probe is a long standing problem of physical chemistry. In this paper a microscopic treatment of this effect is presented. The theory takes into account the modification of the solvent structure around the solute due to this specific interaction between them. It is found that for strong, attractive interaction, there is an enhanced coupling between the solute and the solvent dynamic modes (in particular, the density mode), which leads to a significant increase in the friction on the solute. The diffusion coefficient of the solute is found to depend strongly and nonlinearly on the magnitude of the attractive interaction. An interesting observation is that specific solute-solvent interaction can induce a crossover from a sliplike to a sticklike diffusion. In the limit of strong attractive interaction, we recover a dynamic version of the solvent-berg picture. On the other hand, for repulsive interaction, the diffusion coefficient of the solute increases. These results are in qualitative agreement with recent experimental observations.

High temperature time-dependent low cycle fatigue behaviour of a type 316L(N) stainless steel

Total strain controlled low cycle fatigue tests on 316L(N) stainless steel have been conducted in air at various strain rates in the temperature range of 773-873 K to identify the operative time-dependent mechanisms and to understand their influence on the cyclic deformation and fracture behaviour of the alloy. The cyclic stress response at all the testing conditions was marked by an initial hardening followed by stress saturation. A negative strain rate stress response is observed under specific testing conditions which is attributed to dynamic strain ageing (DSA). Transmission electron microscopy studies reveal that there is an increase in the dislocation density and enhanced slip planarity in the DSA regime. Fatigue life is found to decrease with a decrease in strain rate. The degradation in fatigue resistance is attributed to the detrimental effects associated with DSA and oxidation. Quantitative measurement of secondary cracks indicate that both transgranular and intergranular cracking are accelerated predominantly under conditions conducive to DSA.

Homogeneous isotropic turbulence: large momentum expansion

High temperature expansion is an effective tool for studying second order phase transitions. With this in mind, we have looked at a high momentum expansion for homogeneous isotropic turbulence. Combining our results with those of the inertial range, we give another view of extended self-similarity (ESS).

DC-SIGN and alpha 2,6-sialylated IgG Fc interaction is dispensable for the anti-inflammatory activity of IVIg on human dendritic cells

Intravenous immunoglobulin (IVIg) is widely used to treat autoimmune diseases. Several mutually nonexclusive mechanisms are proposed to explain the beneficial effects of IVIg in patients (1, 2). Lately, Ravetch and colleagues (3) demonstrate that anti-inflammatory activity of IVIg is mediated mainly by antibodies that contain terminal _2,6-sialic acid linkages at the Asn297-linked glycan of Fc region.

Metal-Ion-Dependent Oxidative DNA Cleavage by Transition Metal Complexes of a New Water-Soluble Salen Derivative

A new water-soluble, salen [salen = bis(salicylidene) ethylenediamine]-based ligand, 3 was developed. Two of the metal complexes of this ligand, i.e., 3a, [Mn(III)] and 3b, [Ni(II)], in the presence of cooxidant magnesium monoperoxyphthalate (MMPP) cleaved plasmid DNA pTZ19R efficiently and rapidly at a concentration similar to 1 mu M. In contrast, under comparable conditions, other metal complexes 3c, [Cu(II)] or 3d, [Cr(III)] could not induce any significant DNA nicking. The findings with Ni(II) complex suggest that the DNA cleavage processes can be modulated by the disposition of charges around the ligand.

Satellite-derived direct radiative effect of aerosols dependent on cloud cover

Aerosols from biomass burning can alter the radiative balance of the Earth by reflecting and absorbing solar radiation(1). Whether aerosols exert a net cooling or a net warming effect will depend on the aerosol type and the albedo of the underlying surface(2). Here, we use a satellite-based approach to quantify the direct, top-of-atmosphere radiative effect of aerosol layers advected over the partly cloudy boundary layer of the southeastern Atlantic Ocean during July-October of 2006 and 2007. We show that the warming effect of aerosols increases with underlying cloud coverage. This relationship is nearly linear, making it possible to define a critical cloud fraction at which the aerosols switch from exerting a net cooling to a net warming effect. For this region and time period, the critical cloud fraction is about 0.4, and is strongly sensitive to the amount of solar radiation the aerosols absorb and the albedo of the underlying clouds. We estimate that the regional-mean warming effect of aerosols is three times higher when large-scale spatial covariation between cloud cover and aerosols is taken into account. These results demonstrate the importance of cloud prediction for the accurate quantification of aerosol direct effects.

Orchestration of Haemophilus influenzae RecJ Exonuclease by Interaction with Single-Stranded DNA-Binding Protein

RecJ exonuclease plays crucial roles in several DNA repair and recombination pathways, and its ubiquity in bacterial species points to its ancient origin and vital cellular function. RecJ exonuclease from Haemophilus influenzae is a 575-amino-acid protein that harbors the characteristic motifs conserved among RecJ homologs. The purified protein exhibits a process 5'-3' single-stranded-DNA-specific exonuclease activity. The exonuclease activity of H. influenzae RecJ (HiRecJ) was supported by Mg2+ or Mn2+ and inhibited by Cd2+ suggesting a different mode of metal binding in HiRecJ as compared to Escherichia coli RecJ (EcoRecJ). Site-directed mutagenesis of highly conserved residues in HiRecJ abolished enzymatic activity. Interestingly, substitution of alanine for aspartate 77 resulted in a catalytically inactive enzyme that bound to DNA with a significantly higher affinity as compared to the wild-type enzyme. Noticeably, steady-state kinetic studies showed that H. influenzae single-stranded DNA-binding protein (HiSSB) increased the affinity of HiRecJ for single-stranded DNA and stimulated its exonuclease activity. HiSSB, whose C-terminal tail had been deleted, failed to enhance RecJ exonuclease activity. More importantly, HiRecJ was found to directly associate with its cognate single-stranded DNA-binding protein (SSB), as demonstrated by various in vitro assays, Interaction studies carried out with the truncated variants of HiRecJ and HiSSB revealed that the two proteins interact via the C-terminus of SSB protein and the core-catalytic domain of RecJ. Taken together, these results emphasize direct interactio between RecJ and SSB, which confers functional cooperativity to these two proteins. In addition, these results implicate SSB as being involved in the recruitment of RecJ to DNA and provide insights into the interplay between these proteins in repair and recombination pathways.

Conformational Changes Triggered by Mg2+ Mediate Transactivator Function

Transactivator protein C of bacteriophage mu is essential for the transition from middle to late gene expression during the phage life cycle. The unusual, multistep activation of mom promoter (Pmom) by C protein involves activator-mediated promoter unwinding to recruit RNA polymerase and subsequent enhanced promoter clearance of the enzyme. To achieve this, C binds its site overlapping the -35 region of the mom promoter with a very high affinity, in Mg2+-dependent fashion. Mg2+-mediated conformational transition in C is necessary for its DNA binding and transactivation. We have determined the residues in C which coordinate Mg2+, to induce allosteric transition in the protein, required for the specific interaction with DNA. Residues E26 and D40 in the putative metal binding motif (E26X10D37X2D40) present toward the N-terminus of the protein are found to be important for Mg2+ ion binding. Mutations in these residues lead to altered Mg2+-induced conformation, compromised DNA binding, and reduced levels of transcription activation. Although Mg2+ is widely used in various DNA transaction reactions, this report provides the first insights on the importance of the metal ion-induced allosteric transitions in regulating transcription factor function.

Identifying and addressing equivocal trouble in understanding within classroom interaction

Maintaining intersubjectivity is crucial for accomplishing coordinated social action. Although conversational repair is a recognised defence of intersubjectivity and routinely used to address ostensible sources of trouble in social interaction, it is less clear how people address more equivocal trouble. This study uses conversation analysis to examine preschool classroom interaction, focusing on practices used to identify and address such trouble. Repair is found to be a recurrent frontline practice for addressing equivocal trouble, occasioning space for further information that might enable identifying a specific trouble source. Where further information is forthcoming, a range of strategies are subsequently employed to address the trouble. Where this is not possible or does not succeed, a secondary option is to progress a broader activity-in-progress. This allows for the possibility of another opportunity to identify and address the trouble. Given misunderstandings can jeopardise interactants’ ability to mutually accomplish courses of action, these practices defend intersubjectivity against the threat of equivocal trouble.

Pt metal-CeO2 interaction: Direct observation of redox coupling between Pt-0/Pt2+/Pt4+ and Ce4+/Ce3+ states in Ce0.98Pt0.02O2-delta catalyst by a combined electrochemical and x-ray photoelectron spectroscopy study

Pt ions-CeO2 interaction in Ce1-xPtxO2-delta (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO2 and Ce0.98Pt0.02O2-delta mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt-0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y=0.35) after applying 1.2 V, which is not reversible; Ce0.98Pt0.02O2-delta reaches a steady state with Pt2+:Pt4+ in the ratio of 0.60:0.40 and Ce4+:Ce3+ in the ratio of 0.55:0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2-delta forms a stable electrode for oxidation of H2O to O-2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction in Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt-0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple.

Molecule Modeling of Human Pentameric alpha(7) Neuronal Nicotinic Acetylcholine Receptor and Its Interaction with its Agonist and Competitive Antagonist

The nicotinic Acetylcholine Receptor (nAChR) is the major class of neurotransmitter receptors that is involved in many neurodegenerative conditions such as schizophrenia, Alzheimer's and Parkinson's diseases. The N-terminal region or Ligand Binding Domain (LBD) of nAChR is located at pre- and post-synaptic nervous system, which mediates synaptic transmission. nAChR acts as the drug target for agonist and competitive antagonist molecules that modulate signal transmission at the nerve terminals. Based on Acetylcholine Binding Protein (AChBP) from Lymnea stagnalis as the structural template, the homology modeling approach was carried out to build three dimensional model of the N-terminal region of human alpha(7)nAChR. This theoretical model is an assembly of five alpha(7) subunits with 5 fold axis symmetry, constituting a channel, with the binding picket present at the interface region of the subunits. alpha-netlrotoxin is a potent nAChR competitive antagonist that readily blocks the channel resulting in paralysis. The molecular interaction of alpha-Bungarotoxin, a long chain alpha-neurotoxin from (Bungarus multicinctus) and human alpha(7)nAChR seas studied. Agonists such as acetylcholine, nicotine, which are used in it diverse array of biological activities, such as enhancements of cognitive performances, were also docked with the theoretical model of human alpha(7)nAChR. These docked complexes were analyzed further for identifying the crucial residues involved i interaction. These results provide the details of interaction of agonists and competitive antagonists with three dimensional model of the N-terminal region of human alpha(7)nAChR and thereby point to the design of novel lead compounds.

Size-dependent elasticity of nanocrystalline titania

Synchrotron-based high-pressure x-ray diffraction measurements indicate that compressibility, a fundamental materials property, can have a size-specific minimum value. The bulk modulus of nanocrystalline titania has a maximum at particle size of 15 nm. This can be explained by dislocation behavior because very high dislocation contents can be achieved when shear stress induced within nanoparticles counters the repulsion between dislocations. As particle size decreases, compression increasingly generates dislocation networks hardened by overlap of strain fields that shield intervening regions from external pressure. However, when particles become too small to sustain high dislocation concentrations, elastic stiffening declines. The compressibility has a minimum at intermediate sizes.

Interaction of Co, Mn, Mg and AI with d(GCGTACGC): a spectroscopic study

Spectroscopic study on the interactions of trace elements Co, Mn, Mg and Al with d(GCGTACGC) indicated the following: Al and Mg did not alter T-m values. Mn enhanced T-m at lower concentration and decreased it at higher concentrations. Interestingly Co at higher concentration elevated the T-m. These studies also showed lower concentrations of Mn displaced EtBr, whereas Al could displace it at higher ionic strength. Mg and Co displaced EtBr fluorescence at moderate concentrations. The binding constant values and CD spectra clearly indicated strong binding of these elements to DNA.