Fluorescence, circular dichroism, light scattering, and microscopic characterization of vesicles of sodium salts of three N-acyl peptides

Aggregation behavior of three N-acyl peptide surfactants, sodium N-(4-n-dodecyloxybenzoyl)-L-alyl-L-valinate (SDBAV), L-valyl-L-alaninate (SDBVA), and L-valyl-L-valinate (SDBVV), were investigated. The amphiphiles have very low critical aggregation concentration (cac). Fluorescence anisotropy studies using 1,6-diphenyl-1,3,5-hexatriene (DPH) as a fluorescent probe indicated formation of bilayer aggregates in dilute solution. Transmission electron micrographs showed the existence of large vesicles in dilute solution. Circular dichroism spectra suggested formation of helical aggregates. The vesicle formation was found to be more favored at neutral pH. Dynamic light scattering was used to measure hydrodynamic radius of the vesicles. The microviscosity of the vesicles formed by the amphiphiles was determined by use of fluorescence anisotropy and the lifetime of the DPH probe. The vesicles formed by the surfactants are stable at temperatures above body temperature and for a long period of time. Fluorescence probe studies, however, indicated transformation of vesicles to rod-like micelles at surfactant concentrations much higher than the cac value. Addition of sodium chloride also transformed the vesicles to rod-like micelles.     

Phase Behavior in Mixtures of Cationic Dimeric and Anionic Monomeric Surfactants

The formation of mixed aggregates has been investigated in the mixture of oppositely charged surfactants vastly differing in molecular geometry and size. The systems considered is mixture of the cationic gemini surfactant, ethanediyl-1,2-bis(dodecyldimethylammonium bromide), and anionic surfactant, sodium dodecyl sulfate. Various mixed nano- and microaggregates (micelles, vesicles, thin lamellar sheets, and tubules) were formed depending on bulk composition and total surfactant concentration. Two types of aggregates were found in precipitate, the tubules as prevailing aggregates on the gemini-rich side, and vesicles as prevailing aggregates on the SDS-rich side. The tubules formation was ascribed to mutual influence of specific structure of cationic dimeric surfactant and electrostatic interactions at the bilayer/solution interface. The proposed mechanism involved the formation of lamellar sheets, which rolled-up into tubules.     

Effect of the Bulkiness of the End Functional Amide Groups on the Optical,Gelation, and Morphological Properties of Oligo(p‐phenylenevinylene) π‐Gelators

Herein, we describe the role of end functional groups in the self‐assembly of amide‐functionalized oligo(p‐phenylenevinylene) (OPV) gelators with different end‐groups. The interplay between hydrogen‐bonding and π‐stacking interactions was controlled by the bulkiness of the end functional groups, thereby resulting in aggregates of different types, which led to the gelation of a wide range of solvents. The variable‐temperature UV/Vis absorption and fluorescence spectroscopic features of gelators with small end‐groups revealed the formation of 1D H‐type aggregates in CHCl₃. However, under fast cooling in toluene, 1D H‐type aggregates were formed, whereas slow cooling resulted in 2D H‐type aggregates. OPV amide with bulky dendritic end‐group formed hydrogen‐bonded random aggregates in toluene and a morphology transition from vesicles into fibrous aggregates was observed in THF. Interestingly, the presence of bulky end‐group enhanced fluorescence in the xerogel state and aggregation in polar solvents. The difference between the aggregation properties of OPV amides with small and bulky end‐groups allowed the preparation of self‐assembled structures with distinct morphological and optical features.     

Hydrotropic salt promotes anionic surfactant self-assembly into vesicles and ultralong fibers

Molecular self-assembly has become a versatile approach to create complex and functional nanoarchitectures. In this work, the self-assembly behavior of an anionic surfactant (sodium dodecylbenzene sulfonate, SDBS) and a hydrotropic salt (benzylamine hydrochloride, BzCl) in aqueous solution is investigated. Benzylamine hydrochloride is found to facilitate close packing of surfactants in the aggregates, inducing the structural transformation from SDBS micelles into unilamellar vesicles, and multilamellar vesicles. The multilamellar vesicles can transform into macroscale fibers, which are long enough to be visualized by the naked eye. Particularly, these fibers are robust enough to be conveniently separated from the surfactant solution. The combined effect of non-covalent interactions (e.g., hydrophobic effect, electrostatic attractions, and π-π interactions) is supposed to be responsible for the robustness of these self-assembled aggregates, in which π-π interactions provide the directional driving force for one-dimensional fiber formation.     

Network formation of catanionic vesicles and oppositely charged polyelectrolytes. Effect of polymer charge density and hydrophobic modification

In nonequimolar solutions of a cationic and an anionic surfactant, vesicles bearing a net charge can be spontaneously formed and apparently exist as thermodynamically stable aggregates. These vesicles can associate strongly with polymers in solution by means of hydrophobic and/or electrostatic interactions. In the current work, we have investigated the rheological and microstructural properties of mixtures of cationic polyelectrolytes and net anionic sodium dodecyl sulfate/didodecyldimethylammonium bromide vesicles. The polyelectrolytes consist of two cationic cellulose derivatives with different charge densities; the lowest charge density polymer contains also hydrophobic grafts, with the number of charges equal to the number of grafts. For both systems, polymer-vesicle association leads to a major increase in viscosity and to gel-like behavior, but the viscosity effects are more pronounced for the less charged, hydrophobically modified polymer. Evaluation of the frequency dependence of the storage and loss moduli for the two systems shows further differences in behavior: while the more long-lived cross-links occur for the more highly charged hydrophilic polymer, the number of cross-links is higher for the hydrophobically modified polymer. Microstructure studies by cryogenic transmission electron microscopy indicate that the two polymers affect the vesicle stability in different ways. With the hydrophobically modified polymer, the aggregates remain largely in the form of globular vesicles and faceted vesicles (polygon-shaped vesicles with largely planar regions). For the hydrophilic polycation, on the other hand, the surfactant aggregate structure is more extensively modified: first, the vesicles change from a globular to a faceted shape; second, there is opening of the bilayers leading to holey vesicles and ultimately to considerable vesicle disruption leading to planar bilayer, disklike aggregates. The faceted shape is tentatively attributed to a crystallization of the surfactant film in the vesicles. It is inferred that a hydrophobically modified polyion with relatively low charge density can better stabilize vesicles due to formation of molecularly mixed aggregates, while a hydrophilic polyion with relatively high charge density associates so strongly to the surfactant films, due to strong electrostatic interactions, that the vesicles are more perturbed and even disrupted.     

Interactions of Hemoglobin with Vesicles and Tubes Formed from Mixtures of Histidine-Derived Bolaamphiphile and Conventional Surfactants

The interactions between protein and surfactant aggregates have been the subject of intensive studies due to their potential applications in biological systems. Here we report the interactions of hemoglobin (Hb) with vesicles and tube-like aggregates formed from mixtures of a histidine-derived bolaamphiphile and a cconventional surfactant dodecyltrimethylammonium bromide (DTAB). This study was performed using a combination of UV–vis spectroscopy, steady and synchronous fluorescence spectroscopy, circular dichroism, and microcalorimetry measurements. The secondary structure of the protein is disturbed, and then the partially unfolded protein is capable of penetrating the vesicles and tube-like aggregates, this is mainly the result of hydrogen bonding and hydrophobic interactions between Hb and the H₂D/DTAB aggregates. The polar portion of the unfolded protein chains is near to the polar head of the amphiphile in the aggregate’s membrane. Hb is converted to hemichrome in the vesicles, and the heme monomer is solubilized in tube-like aggregates after escaping from the hydrophobic cavity of Hb.     

Carbodiimide-Driven Dimerization and Self-Assembly of Artificial,Ribose-Based Amphiphiles

The aqueous self-assembly of amphiphiles into aggregates such as micelles and vesicles has been widely investigated over the past decades with applications ranging from materials science to drug delivery. The combination of characteristic properties of nucleic acids and amphiphiles is of substantial interest to mimic biological self-organization and compartmentalization. Herein, we present ribose- and ribonucleotide-based amphiphiles and investigate their self-assembly as well as their fundamental reactivity. We found that various types of aggregates are formed, ranging in size from nanometers to micrometers and all amphiphiles exhibit aggregation-induced emission (AIE) in solution as well as in the solid state. We also observed that the addition of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) leads to rapid and selective dimerization of the amphiphiles into pyrophosphates, which decreases the critical aggregation concentration (CAC) by a factor of 25 when compared to the monomers. Since the propensity for amphiphile dimerization is correlated with their tendency to self-assemble, our results may be relevant for the formation of rudimentary compartments under prebiotic conditions.     

Nucleotides and nucleolipids derivatives interaction effects during multi-lamellar vesicles formation

In this paper a micellar interface, constituted by the cationic surfactant CTAB, in presence of 1,2-epoxydodecane and nucleotides was used for catanionic multi-lamellar vesicles (MLVs) formation. The micellar solution of CTAB is able to disperse the 1,2 epoxydodecane in the micellar core promoting the reaction of this reagent with the nucleotide attracted by the positive surface charge of the micellar aggregates. The alkylation of AMP and UMP nucleotides leads to the synthesis of nucleolipids. The behaviour of the supramolecular structures formed depends on the starting reagents (AMP, UMP and AMP+UMP) and on the assembly capabilities of the products. In particular nucleotides and nucleotides derivatives interaction effects are evaluated during the multi-lamellar vesicles formation. NMR spectroscopy and UV-vis measurements performed on MLVs showed strong aryl interactions. Interestingly, NMR spectra revealed prevailing stacking interactions between complementary nucleolipids. The assembly of complementary nucleotides affects the course of the reaction during the MLVs formation. Moreover the MLVs supramolecular stability has been tested by means of turbidity and UV-vis measurements. In particular, an enhanced stability has been found in systems prepared with complementary nucleotides confirming that in these systems the self-assembly process is influenced by nucleolipids interactions. Furthermore by following the hypocromic effect during the micellar catalysis, we showed that even in the earlier stages of the reaction significant differences are detectable.     

Effect of light on self-assembly of aqueous mixtures of sodium dodecyl sulfate and a cationic, bolaform surfactant containing azobenzene

We report light and small-angle neutron scattering measurements that characterize microstructures formed in aqueous surfactant solutions (up to 1.0 wt % surfactant) containing mixtures of sodium dodecyl sulfate (SDS) and the light-sensitive bolaform surfactant, bis(trimethylammoniumhexyloxy)azobenzene dibromide (BTHA) as a function of composition, equilibration time, and photostationary state (i.e., solutions rich in cis-BTHA or trans-BTHA). We observed formation of vesicles in both SDS-rich and trans-BTHA-rich regions of the microstructure diagram, with vesicles present over a particularly broad range of compositions for trans-BTHA-rich solutions. Illumination of mixtures of BTHA and SDS with a broadband UV light source leads to formation of photostationary states where the fraction of BTHA present as cis isomer (75-80% cis-BTHA) is largely independent of the mixing ratio of SDS and BTHA. For a relatively limited set of mixing ratios of SDS and BTHA, we observed UV illumination of SDS-rich vesicles to result in the reversible transformation of the vesicles to micellar aggregates and UV illumination of BTHA-rich vesicles to result in irreversible precipitation. Surprisingly, however, for many mixtures of trans-BTHA and SDS that formed solutions containing vesicles, illumination with UV light (which was confirmed to lead to photoisomerization of BTHA) resulted in only a small decrease in the number of vesicles in solution, relatively little change in the sizes of the remaining vesicles, and coexistance of the vesicles with micelles. These observations are consistent with a physical model in which the trans and cis isomers of BTHA present at the photostationary state tend to segregate between the different microstructures coexisting in solution (e.g., vesicles rich in trans-BTHA and SDS coexist with micelles rich in cis-BTHA and SDS). The results presented in this paper provide guidance for the design of light-tunable surfactants systems.     

Raman investigation of the CO2 complex formation in CO2-acetone mixtures

Polarized and depolarized Raman spectra of CO2-acetone mixtures have been measured along the isotherm 313 K as a function of CO2 concentration (0.1-0.9 molar fractions in CO2) by varying the pressure from 0.2 up to 8 MPa. Upon CO2 addition, a new band appears at about 655 cm(-1) and is assigned to the lower frequency nu 2(1) component of the bending mode after degeneracy removal due to the formation of a 1:1 electron donor acceptor (EDA) CO2 complex. The equilibrium constant associated with the complex formation was estimated and found close to those of contact charge transfer complexes. The main modifications of the Fermi dyad of CO2 in the mixtures compared with that of pure CO2 at equivalent density have been assessed. The band-shape analysis revealed that each dyad component is described by two Lorentzian profiles, showing that a tagged CO2 molecule probes two kinds of environment in its first shell of neighbors. The first one involves nonspecific interactions of CO2 with surrounding acetone whereas the second is assigned to the signature of 'transient' CO2 complexes formed with acetone. An upper bound life time of the complex has been estimated to be 8 ps. In addition, a broad band has been detected between the Fermi dyad peaks at about 1320 cm(-1) and its origin interpreted as a further evidence of the CO2-acetone heterodimer formation. Finally, the values of the equilibrium concentration of the heterodimer versus the total concentration of CO2 deduced from the analysis of the nu 2(1) band and from the Fermi dyad have been compared, and the difference is interpreted as due to a lack of theoretical approach of Fermi resonance transitions associated with species existing in different environments.     

Supramolecular assemblies of quaternary ammonium cations and halide anions in the gas phase: ESMS-FTICR data and computer modelling

Supramolecular aggregates of tetraalkylammonium halides (R4NX) are formed by electrospray out of acetonitrile solution. Mass spectrometry reveals 88 charged aggregates for R= Me, Et, Bu; X= Br, I, ranging up to [(Bu4N)39Br42]3- in size. With the objective of improving calculations of intermolecular energies for supramolecular aggregates of ions, calibrated semi-empirical potentials for inter-ion interactions have been developed and applied to these aggregates. The accuracy of the calculated energies is supported by the measured collisional dissociation energy of (Et4N+)4 (I-)5. Energy optimisations indicate that the probable structures have the halide ions dispersed in a matrix of cations, which, for Bu4N+, can be mutually attractive. The aggregates are structurally fluid, with multiple structures separated by 4-8 kJmol(-1). The energy calculations are entirely consistent with the observed formation of large aggregates, and of multiply charged anions. It is estimated that the cohesive energies of supramolecular assemblies of ions such as these reach about 40 kJmol(-1) per constituent ion.     

Bilayer vesicles as precursors for spherical fractal aggregates from the self-assembly of a C60-fullerene-dyad in polar solvent

Spherical fractal aggregates of approximately 10 microm were formed from a pi-electronic amphiphile, C(60)-didodecyloxybenzene dyad when extracted from THF into water, necessitating a critical dielectric constant epsilon > or =30 in binary THF-water mixtures. Molecular dynamics simulations revealed the unit cluster to such a form involves an aggregation number approximately 90 with predominant soft associative molecular interactions which corroborated the octadecahedral model proposed for the cluster growth.     

Unusual vesicle-micelle transitions in a salt-free catanionic surfactant: temperature and concentration effects

The spontaneous formation of vesicles by the salt-free surfactant hexadecyltrimethylammonium octylsulfonate (TASo) and the features of an unusual vesicle-micelle transition are investigated in this work. In a previous work, we have shown that this highly asymmetric catanionic surfactant displays a rare lamellar miscibility gap in the concentrated regime. Here, we analyze in detail the aggregation behavior in the dilute regime (less than 3 wt % surfactant) as a function of both concentration and temperature. The phase diagram is dominated by a two-phase region consisting of a dispersion of a swollen lamellar phase (Lalpha') in the excess solvent phase (L1). Stable vesicles form in this two-phase region, and upon temperature increase, a transition to a single solution phase containing only elongated micelles occurs. The structural characterization of the aggregates and the investigation of their equilibrium properties have been carried out by light microscopy, cryo-TEM, water self-diffusion NMR, and SANS. Similarly to the lamellar-lamellar coexistence, the changes in microstructure at high dilution and high temperature can be understood from solubility differences, electrostatic interactions, and preferred aggregate curvature. Surface charge in the aggregates stems from the higher solubility of the octylsulfonate (So-) ion as compared to that of the hexadecyltrimethylammonium ion (TA+). Upon temperature increase, the ratio of free So(-) relative to the neutral TASo increases. Consequently, the surface charge density of the aggregates increases, and this ultimately induces a transition to a higher-curvature morphology (elongated micelles). Vesicles can also be spontaneously formed by cooling solutions from the micellar region, and the mean size obtained is practically independent of cooling rate, suggesting that dissociation/charge effects also control this process.     

Modulating the emission intensity of poly-(9,9-bis(6'-N,N,N-trimethylammonium)hexyl)-fluorene phenylene) bromide through interaction with sodium alkylsulfonate surfactants

The interaction between the cationic HTMA-PFP (Poly-(9,9-bis(6'-N,N,N-trimethylammonium)hexyl-fluorene phenylene) bromide) and oppositely charged sodium n-alkyl sulfonate surfactants of different chain lengths has been studied in DMSO-water solutions (4% v/v) by UV-visible absorption, fluorescence spectroscopy, fluorescence lifetimes, electrical conductivity, and (1)H NMR spectroscopy. Polymer-surfactant interactions lead to complex spectroscopic behaviors which depends on surfactant concentration. At low surfactant concentrations, the observed strong static fluorescence quenching of fluorescence seems to be associated with formation of aggregates between polymer chains neutralized through interaction with surfactants. This is supported by conductivity and by analysis of absorption spectra deconvoluted at each surfactant concentration using an adapted iterative method. In contrast, above the surfactant critical micelle concentration, there is a strong fluorescence enhancement, leading in some cases to higher intensities than in the absence of surfactants. This is attributed to the transformation of the initially formed aggregates into some new aggregate species involving surfactant and polymer. These changes in HTMA-PFP fluorescence as a function of n-alkyl sulfonate concentration are important for the general understanding of polymer-surfactant interactions, and the aggregates formed may be important as novel systems for applications of these conjugated polyelectrolytes.     

Shell-cross-linked vesicles synthesized from block copolymers of Poly(D,L-lactide) and Poly(N-isopropyl acrylamide) as thermoresponsive nanocontainers

A polylactide (D,L-PLA) macroRAFT agent was prepared by utilizing a hydroxyl-functional trithiocarbonate as a coinitiator for the ring-opening polymerization. The length of the resultant polymer was controlled by the concentration of the coinitiator leading to the formation of two PLA polymers with M(n) = 12500 g mol(-)(1) (PDI = 1.46) and M(n) = 20500 g mol(-)(1) (PDI = 1.38) each with omega-trithiocarbonate functionality. Chain extension of PLA via the RAFT (free radical) polymerization of N-isopropyl acrylamide (NIPAAm) resulted in the formation of amphiphilic block copolymers with the PNIPAAm block increasing in size with conversion. TEM measurements of the aggregates obtained by self-organization of the block copolymers in aqueous solutions indicated the formation of vesicles. The sizes of these aggregates were influenced by the ratio of both blocks and the molecular weight of each block. The lower critical solution temperature (LCST) of the block copolymer was largely unaffected by the size of each block. UV turbidity measurements indicated a higher LCST for the block copolymers than for the corresponding PNIPAAm homopolymers. Stabilization of the vesicles was attained by a cross-linking chain extension of the PNIPAAm block using hexamethylene diacrylate. As the trithiocarbonate group was located between the PLA and PNIPAAm blocks, the chain extension resulted in a cross-linked layer between the core and corona of the vesicles.     

Giant vesicles of a single-tailed chiral cationic surfactant, (1R,2S)-(-)-N-dodecyl-N-methylephedrinium bromide, in water

Self-assembly properties of a single-tailed chiral cationic surfactant, (1R,2S)-(-)-N-dodecyl-N-methylephedrinium bromide (DMEB), have been studied in water. The molecular self-assemblies of the amphiphile have been characterized by surface tension, fluorescence probes, light scattering, and microscopic techniques. The results have been compared with those of dodecyltrimethylammonium bromide (DTAB) surfactant. The critical aggregation concentration of DMEB was found to be much less than that of DTAB. Surface tension and fluorescence probe studies have suggested formation of micellar structures at low temperature (<28 degrees C) and spontaneous formation of giant vesicles in water above 28 degrees C. The mean size of the aggregates has been measured by a dynamic light scattering method. The micropolarity and microviscosity of the self-assemblies were determined by fluorescence probe technique. The (1)H NMR and FTIR spectra were recorded to elucidate the role of the hydrophobic head group towards the formation of bilayer structures. The phase transition temperatures of the vesicular aggregates were determined by measurement of fluorescence anisotropy at various temperatures.     

Elucidating driving forces for liposome rupture: external perturbations and chemical affinity

Atomic force microscopy (AFM) studies under aqueous buffer probed the role of chemical affinity between liposomes, consisting of large unilamellar vesicles, and substrate surfaces in driving vesicle rupture and tethered lipid bilayer membrane (tLBM) formation on Au surfaces. 1,2-Distearoyl-sn-glycero-3-phosphoethanolamine-N-poly(ethylene glycol)-2000-N-[3-(2-pyridyldithio) propionate] (DSPE-PEG-PDP) was added to 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) vesicles to promote interactions via Au-thiolate bond formation. Forces induced by an AFM tip leading to vesicle rupture on Au were quantified as a function of DSPE-PEG-PDP composition with and without osmotic pressure. The critical forces needed to initiate rupture of vesicles with 2.5, 5, and 10 mol % DSPE-PEG-PDP are approximately 1.1, 0.8, and 0.5 nN, respectively. The critical force needed for tLBM formation decreases from 1.1 nN (without osmotic pressure) to 0.6 nN (with an osmotic pressure due to 5 mM of CaCl(2)) for vesicles having 2.5 mol % DSPE-PEG-PDP. Forces as high as 5 nN did not lead to LBM formation from pure POPC vesicles on Au. DSPE-PEG-PDP appears to be important to anchor and deform vesicles on Au surfaces. This study demonstrates how functional lipids can be used to tune vesicle-surface interactions and elucidates the role of vesicle-substrate interactions in vesicle rupture.     

Fatty acid vesicles

Results obtained from recent studies on the preparation and application of fatty acid vesicles are reviewed, focusing on some of the particular properties of fatty acid vesicles in comparison with conventional phospholipid vesicles (liposomes): (i) pH dependency which allows reversible transformations from non-vesicular to vesicular aggregates, and (ii) dynamic features that place fatty acid vesicles in between conventional vesicles formed from double-chain amphiphiles and micelles formed from single-chain surfactants. There are two main research areas in which fatty acid vesicles have been studied actively during the last years: (i) basic physico-chemical properties, and (ii) applications as protocell models. Applications of fatty acid vesicles in the fields of food additives and drug delivery are largely unexplored, which is at least partially due to concerns regarding the colloidal stability of fatty acid vesicles (pH- and divalent cation-sensitivity). Recently, fatty acid vesicles were prepared from highly unsaturated fatty acids (docosahexaenoic acid) and the pH range of vesicle formation could be extended to high or low pH values by preparing mixed vesicles through addition of a second type of single-chain amphiphile that stabilizes the vesicle bilayer but itself is not a fatty acid.     

Two-component fibers/gels and vesicles formed from hetero-double-helices of pseudoenantiomeric ethynylhelicene oligomers with branched side chains

A methodology for the formation of fibers/gels and vesicles by molecular assembly and for controlling their properties is presented. Two-component systems of pentamer (P)-5 and tetramer (M)-4 pseudoenantiomeric ethynylhelicenes with decyloxycarbonyl (D) and 4-methyl-2-(2-methylpropyl)-1-pentyloxycarbonyl (bD) side-chains have been examined. Distinct aggregates were formed by changing the solvent for the three combinations of (P)-bD-5/(M)-bD-4, (P)-D-5/(M)-bD-4, and (P)-D-5/(M)-D-4. In toluene, (P)-bD-5/(M)-bD-4, (P)-D-5/(M)-bD-4, and (P)-D-5/(M)-D-4 all formed gels and fibrous assemblies were observed by AFM. The minimum gel-forming concentration (MGC) decreased in the order (P)-bD-5/(M)-bD-4>(P)-D-5/(M)-bD-4>(P)-D-5/(M)-D-4. In diethyl ether, vesicular formation was observed by dynamic light scattering (DLS), AFM, and TEM, and the size of the vesicles decreased in the order (P)-bD-5/(M)-bD-4>(P)-D-5/(M)-bD-4>(P)-D-5/(M)-D-4. Both fiber/gel and vesicle formation were accompanied by enhanced CDs and redshifted UV/Vis absorption bands with a change in color to deep yellow. These are novel two-component oligomeric systems that form assemblies of fibers/gels or vesicles depending on the solvent, and the structures and properties of the assemblies can be fine-tuned by changing the combination of oligomers. In m-difluorobenzene, a homogeneous solution was obtained with (P)-D-5/(M)-bD-4, which again exhibits enhanced CDs and redshifted UV/Vis absorptions. Vapor pressure osmometry analysis showed the formation of a bimolecular heteroaggregate. The study has indicated that pseudoenantiomeric oligomers form hetero-double-helices that hierarchically assemble to form fibers/gels and vesicles.