Bilayer Properties of 1,3-Diamidophospholipids

A series of 1,3-diamido phosphocholines was synthesized, and their potential to form stable bilayers was investigated. Large and giant unilamellar vesicles produced from these new lipids form a wide variety of faceted liposomes. Factors such as cooling rates and the careful choice of the liposome preparation method influence the formation of facets. Interdigitation was hypothesized as a main factor for the stabilization of facets and effectively monitored by small-angle X-ray scattering measurements

Asymmetric Recognition of TRISPHAT Anion. Unusually High Difference in Reactivity of the Pseudoenantiomers of Cinchona Alkaloids

Ammonium cations of cinchonidine- and NOT cinchonine-based alkaloids exert high selectivity towards chiral hexacoordinated TRISPHAT anion

Application of TRISPHAT Anion as NMR Chiral Shift Reagent

TRISPHAT anion 1 is an efficient NMR chiral shift reagent for cationic tris(bisimine)ruthenium(II) complexes

Large-Scale Synthesis and Resolution of TRISPHAT [Tris(tetrachlorobenzenediolato) phosphate(V)] Anion

Both enantiomers of TRISPHAT anion can be obtained on a multigram scale through a novel resolution procedure. The Lambda enantiomer is isolated as the tri-n-butylammonium salt, [(n)()Bu(3)NH][Lambda-1], which is soluble in pure CHCl(3) and CH(2)Cl(2). The Delta enantiomer is prepared as the cinchonidinium derivative, which is only soluble in polar solvent mixtures (>7.5% DMSO in CHCl(3))

Synthesis, Enantiomeric Conformations, and Stereodynamics of Aromatic ortho-Substituted Disulfones

Aromatic ortho-disulfone derivatives are readily accessible from diiodide precursors by Cu(I)-mediated reactions with sodium sulfinate salts. The sulfone substituents adopt C(2)-symmetric enantiomeric conformations (lambda and delta) as evidenced by X-ray structural analysis and (1)H and (31)P NMR on chiral bis(sulfonyl)veratrol derivatives and hexacoordinated tris(benzenediolato)phosphate anions. Slow dynamic conformational isomerism (DeltaG(++) > or = 19.8 kcal mol(-1)) was detected in solution

The synthesis of 1,3-diamidophospholipids

A straightforward synthesis of a small library of 1,3-diamidophospholipids is presented using readily available, cheap reagents and introducing a simple phosphoramidate protecting group strategy

The synthesis of an amine-bearing polymerizable phospholipid

Exchange of the natural glycerol phospholipid backbone with an artificial 1,3-diaminopropanol backbone led to the first synthetic 1,3-diaminophospholipid. The amines in the polar head group region were reacted to acrylamides giving a UV polymerizable phospholipid. Preliminary experiments demonstrate that formulated vesicles can be polymerized into large aggregates of vesicles

Ion Pair Chromatographic Resolution of Tri(diimine)ruthenium(II) Complexes Using TRISPHAT Anions as Resolving Agents

Enantiomers of chiral tris(diimine)ruthenium(II) complexes can be separated on a polar chromatographic phase (SiO2) when associated with TRISPHAT counterions (2 equivalents)

Synthesis, Enantiomeric Conformations, and Stereodynamics of Aromatic ortho-Substituted Disulfones

Aromatic ortho-disulfone derivatives are readily accessible from diiodide precursors by CuI-mediated reaction with sodium sulfinate salts (DMF, 110°). The sulfonyl substituents adopt in solution and in the solid state two enantiomeric conformations (? and d) as evidenced by 31P- and 1H-NMR data of the chiral D3-symmetric tris{4,5-bis[(4-methylphenyl)sulfonyl]benzene-1,2-diolato(2-)-?O,?O}phosphate(v) anion (3a) and 1,2-bis(camphor-10-sulfonyl)-4,5-dimethoxybenzene ((=1,2-bis{{[(1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1-yl]methyl}sulfonyl}-4,5-dimethoxybenzene; 6c). X-Ray structure analysis of 1,2-dimethoxy-4,5-bis(methylsulfonyl)benzene (6a) and 1,2-dimethoxy-4,5-bis(4-methylphenyl)sulfonyl]benzene (6b) confirmed in the solid state the preferred chiral orientation of the sulfonyl groups. Dynamic conformational isomerism was detected for 6c in its 1H-NMR in the temperature range of 110°, the corresponding free energy being 19.8 kcalmol-1