Model of peripheral protein adsorption to the water/lipid interface

Two models have been developed to describe the adsorption of a model peripheral protein, colipase, to phospholipid/diacylglycerol (PL/DG) monolayers. One model is applicable at monolayer collapse pressure and at any composition that exceeds the DG mole fraction of PL/DG lateral complexes (Sugár, I. P.; Mizuno, N. K.; Momsen, M. M.; Brockman, H. L. Biophys. J. 2001, 81, 3387-3397). The other model is applicable at any lateral pressure but only below the mole fraction of DG in the complex (Sugár, I. P.; Mizuno, N. K.; Brockman, H. L. Biophys. J. 2005, 89, 3997-4005). Both models assume that initiation of colipase adsorption to the water/lipid interface requires an area of water-exposed hydrophobic surface that exceeds a critical value. In the first model, accessible surface is provided by the head groups of the uncomplexed DG molecules. This surface area follows a binomial distribution. In the second model, accessible area is created by hydrocarbon chains becoming exposed at the water/lipid interface as total lipid packing density of monolayers of PL and/or PL/DG complexes is decreased. This surface area follows a Poisson distribution. The model described in this paper is a unification, extension, and improvement of these models that is applicable at any lateral pressure and any PL/DG mole fraction. Calculated normalized initial colipase adsorption rates are compared with the available experimental values, and predictions of the adsorption rates are made for currently unmeasured compositions and lateral pressure regimes.     

Cyclic sulfonium salts with S ... O interactions 2. Molecular structures with six-membered rings

1-[2-(N-methylcarbamoyl)phenyl]-3H-2,1-naphto-(1,8-d,e)-oxathiin-1-ium chloride (2), 1-[2-(N-methylcarbamoyl)-phenyl]-2-methyl-3-oxo-3H-1, 2-naphto-(1,8-d,e)-thiazin-1-ium chloride (3), 1-[8-(N-methylcarbamoyl)naphtyl]-2-methyl-3-oxo-3H-1, 2-naphto-(1,8-d,e)-thiazin-1-ium chloride (4) and 1-(8-carboxylatonaphtyl)-2-methyl-3-oxo-3H-1,2-naphto-(1,8-d,e)-thiazin-1-ium dipolar ion (5) cyclic sulfonium salts were prepared and their chemical properties investigated (spirosulfurane-formation, hydrolysis). The molecular structures obtained from x-ray diffraction can be described with a considerably distorted trigonal bipyramidal arrangement of the ligands about the sulfonium center, with O/N—S ... O=apical angles of 173.9, 164.9, 156.6, and 159.0°, as well as with S—O/N apical bond lengths of 1.648, 1.671, 1.664, and 1.682 Å. The structures exhibit relatively short S ... O close contacts with interatomic distances of 2.253, 2.448, 2.795, and 2.619 Å.     

Solute-solvent contact by intermolecular cross relaxation. I. The nature of the water-hydrophobic interface

Intermolecular cross-relaxation rates between solute and solvent were measured by {1H} 19F nuclear magnetic resonance experiments in aqueous molecular solutions of ammonium perfluoro-octanoate and sodium trifluoroacetate. The experiments performed at three different magnetic fields provide frequency-dependent cross-relaxation rates which demonstrate clearly the lack of extreme narrowing for nuclear spin relaxation by diffusionally modulated intermolecular interactions. Supplemented by suitable intramolecular cross-relaxation, longitudinal relaxation, and self-diffusion data, the obtained cross-relaxation rates are evaluated within the framework of recent relaxation models and provide information about the hydrophobic hydration. In particular, water dynamics around the trifluoromethyl group in ammonium perfluoro-octanoate are more retarded than that in the smaller trifluoroacetate.     

Electrophoretic mobility and molecular distribution studies of poly(amidoamine) dendrimers of defined charges

Generation 5 ethylenediamine (EDA)-cored poly(amidoamine) (PAMAM) dendrimers (E5, E denotes the EDA core and 5 the generation number) with different degrees of acetylation and carboxylation were synthesized and used as a model system to investigate the effect of charge and the influence of dendrimer surface modifications on electrophoretic mobility (EM) and molecular distribution. The surface-modified dendrimers were characterized by size-exclusion chromatography, 1H NMR, MALDI-TOF-MS, PAGE, and CE. The focus of our study was to determine how EM changes as a function of particle charge and molecular mass, and how the molecular distribution changes due to surface modifications. We demonstrate that partially modified dendrimers have much broader migration peaks than those of fully surface functionalized or unmodified E5 dendrimers due to variations in the substitution of individual dendrimer surfaces. EM decreased nonlinearly with increases in surface acetylation for both PAMAM acetamides and PAMAM succinamic acids, indicating a complex migration activity in CE separations that is not solely due to charge/mass ratio changes. These studies provide new insights into dendrimer properties under an electric field, as well as into the characterization of dendrimer-based materials being developed for medical applications.     

Regular patterns stabilize auditory streams

The auditory system continuously parses the acoustic environment into auditory objects, usually representing separate sound sources. Sound sources typically show characteristic emission patterns. These regular temporal sound patterns are possible cues for distinguishing sound sources. The present study was designed to test whether regular patterns are used as cues for source distinction and to specify the role that detecting these regularities may play in the process of auditory stream segregation. Participants were presented with tone sequences, and they were asked to continuously indicate whether they perceived the tones in terms of a single coherent sequence of sounds (integrated) or as two concurrent sound streams (segregated). Unknown to the participant, in some stimulus conditions, regular patterns were present in one or both putative streams. In all stimulus conditions, participants' perception switched back and forth between the two sound organizations. Importantly, regular patterns occurring in either one or both streams prolonged the mean duration of two-stream percepts, whereas the duration of one-stream percepts was unaffected. These results suggest that temporal regularities are utilized in auditory scene analysis. It appears that the role of this cue lies in stabilizing streams once they have been formed on the basis of simpler acoustic cues.     

Efficient and connective assembly of highly functionalized benzofurans using o-hydroxyphenones and dichloroethylene

The preparation of highly functionalized benzofurans by a unique and connective transformation is reported. Base-catalyzed condensation of o-hydroxyphenones with 1,1-dichloroethylene generates the corresponding chloromethylene furans. These labile intermediates undergo a facile rearrangement into benzofuran carbaldehydes under mild acidic conditions.