Comparison of liposomes formed by sonication and extrusion: rotational and translational diffusion of an embedded chromophore

We report on the physical and optical characterization of liposomes formed by extrusion and sonication, two widely used methods for vesicle preparation. We also address the issue of whether the properties of bilayers formed from liposomes prepared by the two techniques differ at the molecular and mesoscopic levels. We used the phospholipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), with and without cholesterol, to form liposomes, incorporating 1-oleoyl-2-[12-[(7-nitro-2-1,3-benzoxadiazol-4-yl)amino]dodecanoyl]-sn-glycero-3-phosphocholine (18:1-12:0 NBD-PC) as an optical probe of dynamics. We measured the physical morphology of liposomes by transmission electron microscopy (TEM) and dynamic light scattering (DLS), and the rotational and translational diffusion of 18:1-12:0 NBD-PC by time correlated single photon counting (TCSPC) and fluorescence recovery after pattern photobleaching (FRAPP), respectively. We find that, despite apparent differences in average size and size distribution, both methods of preparation produced liposomes that exhibit the same molecular scale environment. The translational diffusion behavior of the tethered chromophore in planar bilayer lipid membranes formed from the two types of liposomes also yielded similar results.     

12/14/14‐Helix Formation in 2:1 α/β‐Hybrid Peptides Containing Bicyclo[2.2.2]octane Ring Constraints

The highly constrained β‐amino acid ABOC induces different types of helices in β urea and 1:1 α/β amide oligomers. The latter can adopt 11/9‐ and 18/16‐helical folds depending on the chain length in solution. Short peptides alternating proteinogenic α‐amino acids and ABOC in a 2:1 α/β repeat pattern adopted an unprecedented and stable 12/14/14‐helix. The structure was established through extensive NMR, molecular dynamics, and IR studies. While the 1:1 α‐AA/ABOC helices diverged from the canonical α‐helix, the helix formed by the 9‐mer 2:1 α/β‐peptide allowed the projection of the α‐amino acid side chains in a spatial arrangement according to the α‐helix. Such a finding constitutes an important step toward the conception of functional tools that use the ABOC residue as a potent helix inducer for biological applications.     

Solution study of the NF-kappaB p50-DNA complex by UV laser protein-DNA cross-linking

In this study, we describe a new approach for studying protein-DNA interactions in solution. The approach is based on mapping the UV laser-induced protein-DNA cross-links between the amino acids of the protein and the DNA bases that are in direct contact. The approach was applied for studying the solution structure of the human necrosis factor (NF)-kappaB p50 homodimer bound to a 37 base pair DNA. Several points of contact identical to those observed in the NF-kappaB-DNA crystal structure were found between the two biomolecules. Evidence is provided for the occurrence of two new contact points, one for each DNA strand. These new points of contact are located symmetrically a base apart from the extremity of the binding sequence.     

Drap brownien fractionnaire

On définit un processus à deux indices et par intégration fractionnaire d'un bruit blanc. On démontre qu'il est auto-similaire et à accroissements stationnaires, les accroissements étant rectangulaires. On donne quelques propriétés de régularité des trajectoires et la continuité du processus par rapport aux deux paramètres. On obtient un champ aléatoire gaussien de même loi que celui proposé par Anna Kamont, mais notre définition permet de montrer d'autres propriétés, en particulier trajectorielles, et conduit plus aisément à des algorithmes de simulation de tels champs.A random field depending on two parameters and is defined by a fractional integration with respect to the white noise field. Such a process is autosimilar with stationary rectangular increments. The paths have some regular properties, and the process has a sort of regularity with respect of the parameters. The process has the same law as that of Anna Kamont. However, our definition allows to prove some others properties, particularly paths properties, and gives easily simulation algorithms of such of fields.     

Preparation of trimethylsilyl ethers of 3-azetidinols. Scope and Limitations

Preparation of the trimethylsilyl ethers of 1-alkyl-3-azetidinols from non-hindered primary amines and epichlorohydrin by conversion of the intermediate 1-(alkylamino)-3-chloro-2-propanols to their trimethylsilyl ethers by either N-(trimethylsilyl)acetamide or by 1-(trimethylsilyl)imidazole followed by ring closure in acetonitrile is described. This sequence of reactions fails for aromatic amines, but appears to be general for all primary aliphatic amines, although the condensation of hindered amines with epichlorohydrin occurs slowly. Several novel azetidinols, in which the N-alkyl substituent itself contains a second heterocyclic system, are reported. In addition, the pK_A's of several m. and p-substituted 1-benzylazetidinols correlates well with the Hammett equation.     

Crack Singularities for General Elliptic Systems

We consider general homogeneous Agmon‐Douglis‐Nirenberg elliptic systems with constant coefficients complemented by the same set of boundary conditions on both sides of a crack in a two‐dimensional domain. We prove that the singular functions expressed in polar coordinates (r, θ) near the crack tip all have the form r^{k + 1/2}φ(θ) with k ≥ 0 integer, with the possible exception of a finite number of singularities of the form r^k log r φ(θ). We also prove results about singularities in the case when the boundary conditions on the two sides of the crack are not the same, and in particular in mixed Dirichlet‐Neumann boundary value problems for strongly coercive systems: in the latter case, we prove that the exponents of singularity have the form with real η and integer k. This is valid for general anisotropic elasticity too.