Electron density matching as a guide to surfactant design

The effectiveness at reducing interfacial tension between water and different organic solvents was studied, with 14 structurally different dichain sulfosuccinate surfactants. Variations in chemical structure ranged from linear/branched alkyl tail groups, to phenyl-tipped tail units, to partially and fully fluorinated tails. The solvents n-heptane, toluene, and perfluoroheptane were used as example oil phases. Interfacial activity was measured in terms of a reduced interfacial tension scale, R(IFT), based on the value in the presence of surfactants compared to that for the pure solvent-water interface. Overall surfactant chain structure was determined to be the key factor affecting R(IFT). Furthermore, a strong correlation was observed between R(IFT) and the electron density rho(e) of the different surfactants: with any given oil, the most effective surfactants have rho(e) values closest to that for the solvent. For example, phenyl-tipped surfactants were shown to be comparatively more effective at the interface with an aromatic solvent (toluene) than with an aliphatic n-alkane (heptane). Furthermore, fluorination of the tail groups decreased effectiveness at the hydrocarbon/water interface, which was substantially increased at the fluorocarbon/water interface: this too followed the electron density-matching pattern. The importance of chain-tip chemical structure was also noted, with regard to the introduction of phenyl, CF3-, and H-CF2- terminal moieties. For branched alkyl-tailed surfactants, it was found that effectiveness could be linked to an empirical "branching factor". The significance of the electron density matching of organic solvent and surfactant for the prediction of interfacial activities is highlighted, and this concept may prove useful for the future design of new high-efficiency surfactants.     

On conditionally δ-convex functions

Let X be a real vector space, V a subset of X and δ ≧ 0 a given number. We say that f: V → ? is a conditionally δ-convex function if for each convex combination t ₁ υ ₁ + … + t _n υ _n of elements of V such that t ₁ υ ₁ + … + t _n υ _n ∈ V the following inequality holds true: $$ f(t_1 v_1 + \cdots + t_n v_n ) \leqq t_1 f(v_1 ) + \cdots + t_n f(v_n ) + \delta . $$ We prove that f: V → ? is conditionally δ-convex if and only if there exists a convex function $ \tilde f $ : conv V → [?∞, ∞) such that $$ \tilde f(v) \leqq f(v) \leqq \tilde f(v) + \delta for v \in V. $$ In case X = ? ⁿ some conditions equivalent to conditional δ-convexity are also presented.     

Mannose-pepstatin conjugates as targeted inhibitors of antigen processing

The molecular details of antigen processing, including the identity of the enzymes involved, their intracellular location and their substrate specificity, are still incompletely understood. Selective inhibition of proteolytic antigen processing enzymes such as cathepsins D and E, using small molecular inhibitors such as pepstatin, has proven to be a valuable tool in investigating these pathways. However, pepstatin is poorly soluble in water and has limited access to the antigen processing compartment in antigen presenting cells. We have synthesised mannose-pepstatin conjugates, and neomannosylated BSA-pepstatin conjugates, as tools for the in vivo study of the antigen processing pathway. Conjugation to mannose and to neomannosylated BSA substantially improved the solubility of the conjugates relative to pepstatin. The mannose-pepstatin conjugates showed no reduction in inhibition of cathepsin E, whereas the neomannosylated BSA-pepstatin conjugates showed some loss of inhibition, probably due to steric factors. However, a neomannosylated BSA-pepstatin conjugate incorporating a cleavable disulfide linkage between the pepstatin and the BSA showed the best uptake to dendritic cells and the best inhibition of antigen processing.     

The Dynamics of Stretchable Rods in the Inertial Case

Nonlinear amplitude equations for the near-threshold behavior of twisted extensible elastic rods under tension with inertial and dissipative dynamics are derived. In the inertial case localized solutions to the amplitude equations are derived and a linear stability criterion for the pulse solutions is obtained using the Hamiltonian formulation of the problem.     

Observation of proton radioactivity of the (21+) high-spin isomer in 94Ag

We have observed direct one-proton decay of the (21+) isomer in the N=Z nuclide 94Ag into high-spin states in 93Pd by detecting protons in coincidence with gamma-gamma correlations and applying gamma gates based on known 93Pd levels. Two decay branches have been identified, with proton energies of 0.79(3) and 1.01(3) MeV and branching ratios of 1.9(5)% and 2.2(4)%, respectively. The corresponding partial half-life values are 21(6) and 18(4) s. The Q value of the direct proton decay of the (21+) isomer was found to be 5.78(3) MeV. The very small reduced widths of the observed proton decays might reflect dominating collective configurations in the (21+) isomer, and the fine structure of the proton spectrum might indicate a strong deformation of this state.     

Advancing the chromatography of GC/FT-IR to WCOT capillary columns

By the use of a wide-bore WCOT capillary column, it was possible to obtain the first on-the-fly GC/FT-IR spectra with a WCOT column. This wide-bore WCOT column gave improved separation, as compared to a SCOT column, and yielded identifiable infrared spectra for a real sample.     

Oberfl?chenkr?fte und Oberfl?chen-Wechselwirkungen

Ohne Zusammenfassung     

Asymmetric synthesis of dialkyloxy-3-alkylammonium cationic lipids

The cationic diether-linked cytofectin DOTMA (available commercially as a mixture, Lipofectin comprised of DOTMA:DOPE, 1:1) and analogues including DIMRIE and DORIE are frequently used for in vitro and in vivo transfections. Despite this wide usage direct synthetic routes to the optical isomers have received little attention to date. Here we describe strategies to synthesize enantiomers of DOTMA and analogues, including an extremely concise procedure to the trimethylammonium salts. One strategy utilized N-protection, as the imine, with concomitant ether formation and deprotection during the workup. Methylation of the 1-amino-2,3-dialkyloxypropane then generated the trimethylammonium cationic lipids directly. This methodology was extended to synthesize a novel headgroup functionalized lipid. A second route was also developed using an alternative chiral synthon.