Controlling the conformation of oligocholate foldamers by surfactant micelles

Fluorescence resonance energy transfer (FRET) occurred readily in a cholate hexamer labeled with a naphthyl donor and a dansyl acceptor at the chain ends when the hexamer was solubilized by sodium dodecyl sulfate (SDS) micelles in water. Independence of the energy transfer efficiency over 1-70 mM SDS suggested that the energy transfer resulted from the folding of the hexamer instead of its intermolecular aggregation within the micelle. Upon addition of sodium chloride to the solution, energy transfer became less efficient, indicating unfolding of the oligocholate. In contrast, the oligocholate stayed folded in the micelle of nonionic Brij 30, in the presence or absence of NaCl. These results suggested that the oligocholate preferred to fold within the small spherical SDS micelles but unfold when the preference for spherical over rodlike micelles was not strong enough to overcome the tendency for the oligocholate to unfold.     

Effects of amphiphile topology on the aggregation of oligocholates in lipid membranes: macrocyclic versus linear amphiphiles

A macrocyclic and a linear trimer of a facially amphiphilic cholate building block were labeled with a fluorescent dansyl group. The environmentally sensitive fluorophore enabled the aggregation of the two oligocholates in lipid membranes to be studied by fluorescence spectroscopy. Concentration-dependent emission wavelength and intensity revealed a higher concentration of water for the cyclic compound. Both compounds were shown by the red-edge excitation shift (REES) to be located near the membrane/water interface at low concentrations, but the cyclic trimer was better able to migrate into the hydrophobic core of the membrane than the linear trimer. Fluorescent quenching by a water-soluble (NaI) and a lipid-soluble (TEMPO) quencher indicated that the cyclic trimer penetrated into the hydrophobic region of the membrane more readily than the linear trimer, which preferred to stay close to the membrane surface. The fluorescent data corroborated with the previous leakage assays that suggested the stacking of the macrocyclic cholate trimer into transmembrane nanopores, driven by the strong associative interactions of water molecules inside the macrocycles in a nonpolar environment.     

Solid state and solution conformation of 2-pyridinecarboxylic acid hydrazides: a new structural motif for foldamers

X-Ray crystallography and NMR show a strong preference for trans conformers of N′-phenyl or N′-(2-pyridyl) 2-pyridinecarboxylic acid hydrazides, stabilized by an NHN_pyr. intramolecular hydrogen bond both in the solid state and in solution. This allows us to extrapolate that oligomers of this unit should adopt extended linear conformations.     

Surface and micelle properties of novel multi-dentate surfactants

Novel multi-dentate surfactants, based on alkyl amines of varying hydrophobicity were synthesized, and molecular structures were characterized by IR, UV-vis, NMR and FAB-MS. The new surfactants have good water solubility and are highly efficient at reducing aqueous surface tension. Small-angle neutron scattering (SANS) studies were carried out with aqueous solutions in D(2)O to study aggregation. Spherical micelles were shown to form, and these grow with increasing alkyl chain length; their conformation is unusual compared to conventional linear chain surfactants.     

Conformational rigidity and dielectric properties of polyimides

On the basis of two series of polyimides it was shown that the conformational rigidity and the presence of side voluminous substituents determine the packing of macromolecular chains in glassy state. The presence of hexafluoroisopropylidene groups leads to the increase of free volume of polymers due to the repulsion of such groups belonging to different macromolecular chains. The physical properties studied here, such as dielectric permittivity and electrets properties depend on the size of free volume. The normalized surface potential is determined by the mass fraction of fluorine content and by the conformational rigidity of those polymers.     

Aromatic foldamers with iminodicarbonyl linkers: their structures and optical properties

[structure: see text] Carboxamides possessing naphthalene rings connected by multiple iminodicarbonyl linkers were synthesized. These molecules forced the naphthalene rings to be placed in the positions facing each other, and they form helical foldamers both in solution and in the crystalline state. Their folding structures were investigated by single-crystal X-ray analysis and (1)H NMR spectroscopy. Their absorption and fluorescence spectra showed a red shift as the number of naphthalene moieties increased. This remarkable change is based on the intramolecular interaction between naphthalene moieties. Helicity of the foldamer can be controlled by the introduction of chiral auxiliaries at imide nitrogen atoms, which results in an observation of induced circular dichroism.     

Influence of conformational rigidity on membrane properties of polyimides

Several polyimides were studied with regard to the influence of their conformational rigidity on the packing in glassy state, and consequently on their physical properties such as glass transition temperature and selectivity of gas separation membranes made from these polymers. The values of their physical properties were taken from literature, while the conformational rigidity parameters such as Kuhn segment, characteristic ratio, and occupied, free, and accessible volumes were calculated here and were correlated with physical properties. It was shown that there are correlations between selectivity of gas separation membranes made from these polyimides on one hand, and characteristic ratio, on another hand.     

Rotary friction,dipole moments,conformation and rigidity of polybutylisocyanate molecules in solution

Experimental data on the dependence of the rotatory diffusion coefficients and dipole moments on molecular weight and the theory of hydrodynamic properties and of the size of wormlike chains were used for determining the main conformational characteristics of the polyisocyanate chain S is the number of molecular units in a segment, λ is the length of the projection of the monomer unit on the axis of the molecule, and μ_o is the dipole moment of the monomer unit. The values of S and λ agree with those found previously by hydrodynamic methods. It was shown that the flat cis-structure of the polyisocyanate chain corresponds to values of λ = 2 × 10^?8cm andμ_o = 1·8D. Analysis of experimental data indicates that dimensions of “geometrical” and “electrical” segments in the PBIC chain are identical.     

Effect of micelle structure on the spectral properties of poly(dimethylsilylene)

The absorption and fluorescence spectral features of an intractable poly(silylene), poly(dimethylsilylene) (1), in aqueous micelles--attributable to an elongated transoid backbone conformation encompassed by three micelles--are discussed.     

Aggregation and assembly of crescent foldamers

Recent studies have started to provide initial insights into the aggregation and assembly of two classes of back-rigidified foldamers with flat,curved backbones consisting of aromatic residues.With their persistent shape that presents large,well-defined aromatic surface areas,these crescent foldamers were found to undergo size-dependent aggregation in solution and pack into 1D assemblies in the solid state.Crescent aromatic oligoamides undergo stacking interactions not only in polar solvents but also in non...     

Effects of ligands and spin-polarization on the preferred conformation of distannynes

Recent experimental and theoretical evidence has shown that distannynes, RSnSnR, can adopt either a singly bonded or a multiply bonded structure. Within calculations on small models, such as MeSnSnMe, apparently dramatic differences in conformational preference have been reported. We show that these differences arise due to the treatment of spin-polarization in density functional theory (DFT), and review stability analysis; a diagnostic for the need to include spin-polarization. The low-energy singly bonded structure can only be reached when spin-polarization is allowed. Additional DFT calculations on PhSnSnPh show that the singly bonded structure is the global minimum, leading to a flat torsional potential. The role of electronic effects is further probed by changing the donor-acceptor properties of R. Implications for the structural preference of experimentally synthesized species are discussed.     

Thorpe-Ingold effect on the conformation and photophysical properties of dialkylsilylene-spaced divinylarene copolymers

Geminal disubstitution on silicon in dialkylsilylene-spaced divinylarene copolymers may dictate the conformation and photophysical properties of the copolymers, bulky (i)Pr substituted copolymers being more folded than Me substituent analogues.     

Mechanical properties of block copolymer vesicle and micelle modified epoxies

Block copolymers with and without reactive functionalities can improve fracture resistance in brittle epoxies even when added in relatively small amounts (<5 wt %). At certain compositions, amphiphilic block copolymers spontaneously self‐assemble into vesicles, spherical micelles, or wormlike micelles in thermoset resins, and these morphologies are retained with the full curing of the resins. The addition of such block copolymers leaves the glass‐transition temperature of these blends relatively unchanged, whereas the fracture resistance increases up to a factor of 3.5 for the vesicle‐modified blends. For epoxies modified with block copolymers self‐assembled into a spherical geometry (vesicles or spherical micelles), the fracture resistance scales with the ratio of the interparticle distance to the average vesicle (or spherical micelle) diameter (D_i/D_p) and increases as this quantity is reduced. Greater adhesion between the vesicle and epoxy resin improves the fracture resistance only at higher values of D_i/D_p, at which the materials are more brittle. Debonding and subsequent matrix plastic deformation are identified as the toughening mechanisms in these blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2444–2456, 2003     

A new class of foldamers based on cis-gamma-amino-L-proline

A synthetic method for the preparation of conformationally constrained gamma-peptides derived from gamma-amino-L-proline is described. The methodology allows the independent buildup of the peptide backbone and the introduction of sequential variations by reactions with the alpha-amino group of gamma-aminoproline. Both alkyl- and acyl-substituted gamma-peptides have been prepared and studied by CD and NMR. Conformational restrictions due to the cyclic structure of the monomer give rise to long-range interactions that are indicative of secondary structures even in aqueous solution. Interresidue NOEs suggest a concatenation of turns that, in a permissive solvent, could give rise to an isolated hydrogen bond ribbon, flanked and protected by proline rings.     

Asymmetric reduction of aromatic ketones: importance of the conformation of the aromatic group

Some aromatic ketones have been reduced by borane or by catecholborane using oxazaborolidine as a catalyst. It has been found that, when borane is used, the enantiomeric excess of alcohol produced decreases as the substitution on the ortho position of benzene ring increases. However, for ketones with 2,6-disubstituted aryl substituents the enantiomeric excess increases when catecholborane is used.     

Co-solvent effects on drag reduction, rheological properties and micelle microstructures of cationic surfactants

Some quaternary cationic surfactants, when mixed with a counterion, are known to self-assemble into threadlike micelles in water. Such behavior causes drastic changes in rheological properties of even very dilute solutions, allowing them to be used as drag reducing agents (DRA) in turbulent pipe flow circulating systems, such as district cooling/heating systems. Surfactant self-assembly is a physicochemical phenomenon whose character depends on surfactant nature and concentration, nature of the solvent, temperature and type and concentration of counterions. This study investigates drag reduction (DR) and rheological properties of two cationic surfactants, Ethoquad O/12 (oleyl bis(hydroxyethyl)methylammonium chloride) and Ethoquad O/13 (oleyl tris(hydroxyethyl) ammonium acetate), with excess salicylate counterion (NaSal), in mixed solvents containing 0 to 28 wt% ethylene glycol (EG) and water. The addition of EG to the solvent had greater effects on solutions' DR ability, shear viscosity, apparent extensional viscosity and viscoelasticity at 25 degrees C than at approximately 0 degrees C. Cryo-TEM images show threadlike micelle in these systems. DR at low temperatures in solutions containing moderate amount of EG can be utilized in a new approach to energy saving in district cooling systems using EG-water based mixtures as the cooling fluids.     

Synthesis of poly(dipeptide)s on the surface of functional micelle and reversed micelle

Amphiphilic active 4-dodecanoyl-2-nitrophenyl esters of dipeptide containing β-alanine ( 1 – 5 ) were prepared and their polycondensation was studied in detail. The critical micelle concentrations of the active esters 1 – 5 were determined in water by the dye method and the apparent mean aggregation number of reversed micelles formed by model compound 6 was determined by the osmotic method. The results of polycondensation can be explained by assuming that aggregations such as micelle and reversed micelle play an important role in polycondensation. The obtained new poly(dipeptide)s were examined by IR, ¹H NMR, x-ray diffraction, and circular dichroism spectra.