Effects of chemical modification of sphingomyelin ammonium group on formation of liquid-ordered phase.

Sphingomyelin (SM) and cholesterol form microdomains called lipid rafts in cellular membranes. To develop a versatile fluorescent lipid probe, chemical modifications to both the hydrophobic and hydrophilic portions of SM are essential. Few reports describing SM probes with a fluorophore at the polar head group have been published. This study examined the effect of substitution on an ammonium moiety of SM on the membrane properties of SM. Two SM analogs with small propargyl and allyl groups on the quaternary nitrogen atom were synthesized and subjected to analysis using differential scanning calorimetry, fluorescent anisotropy, detergent solubilization, surface pressure, and density measurements. Results demonstrated that the two SM analogs retained the membrane properties of SM, including formation of an ordered phase and the ability to interact with cholesterol. A dansyl-substituted SM was prepared for fluorescent measurements. Dansyl-SM showed less of a propensity to form microdomains. These findings imply the potential application of N-substituted SMs as a raft-specific molecular probe.

Stereoselective preparation of ß,γ-methano-GABA derivatives.

The Kulinkovich-de Meijere reaction between an unsaturated Grignard reagent and a chiral amide takes place with a high trans stereoselectivity and provides a convenient access to non-racemic trans cyclopropylamines. These compounds are transformed in four steps into the corresponding N-protected ß,γ-methano-GABA derivatives, which are obtained for the first time in enantiomerically pure form. The corresponding transformations of the cis cyclopropylamine adducts are also described.

Characterization of the ordered phase formed by sphingomyelin analogues and cholesterol binary mixtures.

The influences of structural alterations of sphingomyelin (SM) on its interactions with cholesterol (chol) and on ordered phase formation were examined by density measurements and surface pressure vs. molecular area isotherm measurements. In addition, we quantitatively characterized the ordered phase formed in each SM and chol binary mixture on the basis of the molecular compressional modulus of SM ( [Formula: see text]). Density measurements demonstrated that the ordered phase formation in threo-SM (tSM)/chol and dihydrosphingomyelin (DHSM)/chol binary bilayers shows similar chol concentration-dependency to that of natural erythro-SM (eSM)/chol bilayers; the ordered phase formation was completed in the presence of 25 mol% chol. In contrast, SM bearing a triple bond in the place of a double bond (tripleSM) required a greater concentration of chol to completely transform the bilayer into the ordered phase (at 40 mol% chol). Surface pressure vs. molecular area isotherms showed that the DHSM molecule ( [Formula: see text] = 290 mN/m) is more rigid than eSM ( [Formula: see text] = 240 mN/m) above 30 mol% chol (in the ordered phase), although these values are similar (140-150 mN/m) in the absence of chol (liquid condensed phase). Most likely, the DHSM/chol mixture forms a more ordered membrane than the eSM/chol mixture does. Moreover, in the absence of chol, the rigidity of the tripleSM molecule ( [Formula: see text] = 250 mN/m) is significantly higher as compared with that of the eSM molecule ( [Formula: see text] = 150 mN/m), which is probably due to the presence of a triple bond.

Expeditive syntheses of functionalized pentahelicenes and NC-AFM on Ag(001).

One of the shortest and most efficient routes toward a series of functionalized pentahelicenes is reported. Benzylic (dibromo)methine coupling is an important entry into functional helicene chemistry. It allowed a mono- or a double functionalization by some metal-catalyzed Ar-C, Ar-S, Ar-CN, and Ar-I bond formations. Those functions offer new avenues for further applications. For instance, helicene (4) can be supported on a Ag(001) surface, which was characterized by high-resolution NC-AFM imaging.