Structural Characterization of Pluronic Micelles Swollen with Perfume Molecules.

The insertion in nonionic polymer micelles (Pluronics F127) of seven essential oils and some of the pure compounds that compose them was investigated by complementary differential scanning calorimetry, small-angle X-ray, and neutron scattering (SAXS and SANS). The study revealed various insertion and swelling behaviors for the different oil molecules, an evidence of different interaction mechanisms involved between oils and Pluronic monomers. Thermodynamically, the addition of oil increased the micellization enthalpy due to an enhanced release of water molecules, leading subsequently to a decrease of the critical micellar temperature (CMT). Structurally, with oil, SANS revealed the presence of large aggregates at lower temperature than the CMT for which their size is maximal. Above the CMT, the size decreased and the equilibrium was reached a few degrees after the temperature corresponding to the maximum of the endothermic peak. At 37 °C, the detailed combined SANS and SAXS analysis demonstrated a partial phase separation between the oil and the poly(propylene oxide) core. The hydrophilic stabilizing poly(ethylene oxide) shell remains unchanged.

Polymer loaded microemulsions: Changeover from finite size effects to interfacial interactions.

Form fluctuations of microemulsion droplets are observed in experiments using dielectric spectroscopy (DS) and neutron spin echo spectroscopy (NSE). Previous work on dioctyl sodium sulfosuccinate based water in oil microemulsions in the droplet phase has shown that adding a water soluble polymer (Polyethylene glycol M = 1500 g mol-1) modifies these fluctuations. While for small droplet sizes (water core radius rc < 37 Å) compared to the size of the polymer both methods consistently showed a reduction in the bending modulus of the surfactant shell as a result of polymer addition, dielectric spectroscopy suggests the opposite behaviour for large droplets. This observation is now confirmed by NSE experiments on large droplets. Structural changes due to polymer addition are qualitatively independent of droplet size. Dynamical properties, however, display a clear variation with the number of polymer chains per droplet, leading to the observed changes in the bending modulus. Furthermore, the contribution of structural and dynamical properties on the changes in bending modulus shifts in weight. With increasing droplet size, we initially find dominating finite size effects and a changeover to a system, where interactions between the confined polymer and the surfactant shell dominate the bending modulus.

Self-assembling peptide/thermoresponsive polymer composite hydrogels: effect of peptide-polymer interactions on hydrogel properties.

We have investigated the effect of doping the self-assembling octapeptide FEFEFKFK (F, phenylalanine; E, glutamic acid; K, lysine) hydrogels with various amounts of thermoresponsive conjugate of FEFEFKFK and poly(N-isopropylacrylamide) (PNIPAAm) in order to create novel hydrogels. The samples were characterized using a range of techniques including microdifferential scanning calorimetry (µDSC), oscillatory rheology, transmission electron microscopy (TEM), atomic force microscopy (AFM), and small angle neutron scattering (SANS). The peptide from the conjugate was shown to be incorporated into the peptide fiber, resulting in the polymer being anchored to the peptide fiber. The conjugation of the polymer to the peptide and its anchoring to the peptide fibers did not affect its lower critical solution temperature (LCST). On the other hand, it did result in a decrease in the LCST enthalpy and a significant increase in the G' of the hydrogels, suggesting the presence of hydrogen bond interactions between the peptide and the polymer. As a result, the polymer was found to adopt a fibrillar arrangement tightly covering the peptide fiber. The polymer was still found to go through a conformational change at the LCST, suggesting that it collapses onto the peptide fiber. On the other hand, the fibrillar network was found to be mainly unaffected by the polymer LCST. These changes at the LCST were also found to be fully reversible. The nature of the interaction between the polymer and the peptide was shown to have a significant effect on the conformation adopted by the polymer around the fibers and the mechanical properties of the hydrogels.

Ion specific effects in trivalent counterion induced surface and solution self-assembly of the anionic surfactant sodium polyethylene glycol monododecyl ether sulfate.

The effect of different trivalent counterions, Al(3+), Cr(3+), Sc(3+), Gd(3+), and La(3+), on the surface adsorption and Al(3+), Cr(3+), and Sc(3+) for solution self-assembly of the anionic surfactant sodium polyethylene glycol monododecyl ether sulfate has been studied by neutron reflectivity and small angle neutron scattering. The strong binding and complexation between the trivalent counterions and the anionic surfactant result in significant micellar growth and the formation of surface multilayer structures at the air-water interface at relatively low counterion concentrations. Broadly similar surface and solution behaviors are observed for the different trivalent counterions. The evolution in the surface and solution structures in detail depends upon the nature of the counterion, its hydrated radius and its strength of binding. Exceptionally the addition of Cr(3+) counterions have a less pronounced effect. This is attributed to a greater reluctance for exchange within the primary hydration shell for Cr(3+) ions, which results in a shielding of the electrostatic interactions and a reduced surfactant-counterion binding.

Correlation between the geometrical shape and growth behaviour of surfactant micelles investigated with small-angle neutron scattering.

The correlation between the growth behaviour and geometrical shape for CTAB-rich mixed micelles formed by the cationic surfactant hexadecyl trimethyl ammonium bromide (CTAB) and the anionic surfactant sodium octyl sulphate (SOS) has been investigated with small-angle neutron scattering (SANS). Small tablet-shaped micelles formed by CTAB are found to grow only weakly in size with increasing surfactant concentration. The extent of growth becomes increasingly stronger as the fraction of SOS is increased. At higher fractions of SOS, a rather weak growth at low surfactant concentrations is followed by a sharp increase in aggregation numbers beyond a certain surfactant concentration. Such an abrupt transition from weakly to strongly growing micelles has been observed in the past for several micellar systems and is usually referred to as the second critical micelle concentration. The growth behaviour has been rationalized from a theoretical point of view by means of employing the recently developed general micelle model. The theory excellently predicts micellar growth behaviours as well as the observed correlation between the geometrical shape and micellar growth. In accordance, both width and length are found to slightly increase for weakly growing tablet-shaped micelles. On the other hand, strongly growing micelles that are observed above the second cmc display a completely different behaviour, according to which the length increases considerably while the width of the micelles decreases. Most interestingly, by means of optimizing the agreement between the general micelle model and experimentally determined aggregation numbers, we are able to determine the three bending elasticity constants: spontaneous curvature, bending rigidity and saddle-splay constant.

Form fluctuations of polymer loaded spherical microemulsions studied by neutron scattering and dielectric spectroscopy.

We investigate the structure and shell dynamics of the droplet phase in water/AOT/octane microemulsions with polyethyleneglycol (MW = 1500) molecules loaded in the droplets. Size and polydispersity of the droplets is determined with small angle X-ray scattering and small angle neutron scattering experiments. Shell fluctuations are measured with neutron spin echo spectroscopy and related to the dynamic percolation seen in dielectric spectroscopy. Shell fluctuations are found to be well described by the bending modulus of the shell and the viscosities inside and outside the droplets. Addition of the polymer decreases the modulus for small droplets. For large droplets the opposite is found as percolation temperature shifts to higher values.

Impact of AlCl3 on the self-assembly of the anionic surfactant sodium polyethylene glycol monoalkyl ether sulfate in aqueous solution.

Small-angle neutron scattering has been used to study the self-assembly of the anionic surfactant sodium polyethylene glycol monoalkyl ether sulfate in aqueous solution and in the presence of Al(3+) multivalent counterions in the form of AlCl3. The addition of the Al(3+) ions promotes significant micellar growth of the initially globular micelles into highly elongated structures until ultimately lamellar structures form. Increasing the size of the polyethylene oxide, EO, group progressively suppresses micellar growth before lamellar formation. Reducing the alkyl chain length has a similar effect on the structural evolution. Both trends are associated with increased solubility with increasing EO group size and decreasing alkyl chain length. Both the size of the EO group and the length of the alkyl chain affect sodium diethylene glycol monododecyl ether sulfate/Al(3+) complex formation and drive lamellar formation to progressively higher AlCl3 concentrations.

Influence of calcium ions on rhamnolipid and rhamnolipid/anionic surfactant adsorption and self-assembly.

The impact of Ca(2+) counterions on the adsorption at the air-water interface and self-assembly in aqueous solution of the rhamnolipid biosurfactant and its mixture with the anionic surfactant sodium dodecylbenzenesulfonate, LAS, has been studied using neutron reflectometry and small-angle neutron scattering. The results illustrate how rhamnolipids are calcium tolerant and how their blending with conventional anionic surfactants improves the calcium tolerance of the anionic surfactant. Ca(2+) has relatively little effect upon the adsorption and self-assembly of the monorhamnose, R1, and dirhamnose, R2, rhamnolipids, even at high pH, due to their predominantly nonionic nature. For R1/R2 mixtures the addition of Ca(2+) has little impact upon the adsorbed amount or the surface composition. For R2/LAS mixtures the addition of Ca(2+) results in an increased adsorption and a surface slightly richer in R2. The weak binding of Ca(2+) to R1 and R2 does result in a change to the degree of ionization of the micelles and especially for mixed R1/R2 micelles at R1-rich solution compositions. The stronger binding of Ca(2+) to LAS results in the addition of Ca(2+) having a much greater impact on the self-assembly of R1/LAS and R2/LAS mixtures. For R1/LAS mixtures the addition of Ca(2+) promotes the formation of more planar structures, even at low surfactant concentrations where in the absence of Ca(2+) mixed globular micelle formation dominates. In R2/LAS mixtures, where there is a greater contrast between the high and low preferred curvatures associated with R2 and LAS, the addition of Ca(2+) results in a more complex evolution in micellar aggregation and the degree of ionization of the micelles. This results in variations in Ca(2+) binding that promotes micellar structures in which a spatial segregation of the two surfactant components within the micelle occurs.

The effect of size ratio on the sphere structure factor in colloidal sphere-plate mixtures.

Binary mixtures of colloidal particles of sufficiently different sizes or shapes tend to demix at high concentration. Already at low concentration, excluded volume interactions between the two species give rise to structuring effects. Here, a new theoretical description is proposed of the structure of colloidal sphere-plate mixtures, based on a density expansion of the work needed to insert a pair of spheres and a single sphere in a sea of them, in the presence or not of plates. The theory is first validated using computer simulations. The predictions are then compared to experimental observations using silica spheres and gibbsite platelets. Small-angle neutron scattering was used to determine the change of the structure factor of spheres on addition of platelets, under solvent contrast conditions where the platelets were invisible. Theory and experiment agreed very well for a platelet/sphere diameter ratio D∕d = 2.2 and reasonably well for D∕d = 5. The sphere structure factor increases at low scattering vector Q in the presence of platelets; a weak reduction of the sphere structure factor was predicted at larger Q, and for the system with D∕d = 2.2 was indeed observed experimentally. At fixed particle volume fraction, an increase in diameter ratio leads to a large change in structure factor. Systems with a larger diameter ratio also phase separate at lower concentrations.

Dysmyelination and glycolipid interference caused by phenylalanine in phenylketonuria.

Phenylketonuria (PKU) is a metabolic disorder connected to an excess of phenylalanine (Phe) in the blood and tissues, with neurological consequences. The disease's molecular bases seem to be related to the accumulation of Phe at the cell membrane surface. Radiological outcomes in the brain demonstrate decreased water diffusivity in white matter, involving axon dysmyelination of not yet understood origin. We used a biophysical approach and model membranes to extend our knowledge of Phe-membrane interaction by clarifying Phe's propensity to affect membrane structure and dynamics based on lipid composition, with emphasis on modulating cholesterol and glycolipid components to mimic raft domains and myelin sheath membranes. Phe showed affinity for the investigated membrane mimics, mainly affecting the Phe-facing membrane leaflet. The surfaces of our neuronal membrane raft mimics were strong anchoring sites for Phe, showing rigidifying effects. From a therapeutic perspective, we further investigated the role of doxycycline, known to disturb Phe packing, unveiling its action as a competitor in Phe interactions with the membrane, suggesting its potential for treatment in the early stages of PKU. Our results suggest how Phe accumulation in extracellular fluids can impede normal growth of myelin sheaths by interfering with membrane slipping and by remodulating free water and myelin-associated water contents.

Self-assembly of mixed anionic and nonionic surfactants in aqueous solution.

We present the phase diagram and the microstructure of the binary surfactant mixture of AOT and C(12)E(4) in D(2)O as characterized by surface tension and small angle neutron scattering. The micellar region is considerably extended in composition and concentration compared to that observed for the pure surfactant systems, and two types of aggregates are formed. Spherical micelles are present for AOT-rich composition, whereas cylindrical micelles with a mean length between 80 and 300 Å are present in the nonionic-rich region. The size of the micelles depends on both concentration and molar ratio of the surfactant mixtures. At higher concentration, a swollen lamellar phase is formed, where electrostatic repulsions dominate over the Helfrich interaction in the mixed bilayers. At intermediate concentrations, a mixed micellar/lamellar phase exists.

Self-assembly of hydrophobin and hydrophobin/surfactant mixtures in aqueous solution.

The self-assembly of the protein hydrophobin, HFBII, and its self-assembly with cationic, anionic, and nonionic surfactants hexadecylterimethyl ammonium bromide, CTAB, sodium dodecyl sulfate, SDS, and hexaethylene monododecyl ether, C(12)E(6), in aqueous solution have been studied by small-angle neutron scattering, SANS. HFBII self-assembles in solution as small globular aggregates, consistent with the formation of trimers or tetramers. Its self-assembly is not substantially affected by the pH or electrolytes. In the presence of CTAB, SDS, or C(12)E(6), HFBII/surfactant complexes are formed. The structure of the HFBII/surfactant complexes has been identified using contrast variation and is in the form of HFBII molecules bound to the outer surface of globular surfactant micelles. The binding of HFBII decreases the surfactant micelle aggregation number for increasing HFBII concentration in solution, and the number of hydrophobin molecules bound/micelle increases.

The adsorption and self-assembly of mixtures of alkylbenzene sulfonate isomers and the role of divalent electrolyte.

In this paper, the role of the different structural isomers of the anionic surfactant sodium para-dodecyl benzene sulfonate, LAS, on surface adsorption and solution self-assembly has been studied. Using a combination of neutron reflectivity, NR, and small angle neutron scattering, SANS, the effect of mixing an isomer with a short symmetric hydrocarbon chain with one which has an asymmetric hydrocarbon chain on both the equilibrium surface adsorption behavior and the solution microstructure of the mixtures, both in the presence and absence of a divalent cation (Ca(2+)), has been investigated. In the absence of electrolyte, the LAS isomer mixtures form small charged globular micelles throughout the composition range studied. The micelle aggregation number increases with the increase in the asymmetric isomer content, reflecting an increase in the packing efficiency within the micelle. The addition of calcium ions promotes the formation of planar aggregates, as multilamellar vesicles, but only when the symmetric LAS isomer is the major component of the mixture. At a surfactant concentration just above the critical micelle concentration, CMC, and in the absence of electrolyte, the variation in the surface composition is close to the solution composition. Regular solution theory, RST, calculations show that this variation is also close to what is expected for ideal mixing. The addition of Ca(2+) ions induces a different surface behavior, resulting in the formation of multilayer structures at the interface throughout the entire composition range.

Solution self-assembly of the sophorolipid biosurfactant and its mixture with anionic surfactant sodium dodecyl benzene sulfonate.

The self-assembly in aqueous solution of the acidic (AS) and lactonic (LS) forms of the sophorolipid biosurfactant, their mixtures, and their mixtures with anionic surfactant sodium dodecyl benzene sulfonate, LAS, has been studied using predominantly small-angle neutron scattering, SANS, at relatively low surfactant concentrations of <30 mM. The more hydrophobic lactonic sophorolipid forms small unilamellar vesicles at low surfactant concentrations, in the concentration range of 0.2 to 3 mM, and transforms via a larger unilamellar vesicle structure at 7 mM to a disordered dilute phase of tubules at higher concentrations, 10 to 30 mM. In marked contrast, the acidic sophorolipid is predominantly in the form of small globular micelles in the concentration range of 0.5 to 30 mM, with a lower concentration of larger, more planar aggregates (lamellar or vesicular) in coexistence. In mixtures of AS and LS, over the same concentration range, the micellar structure associated with the AS sophorolipid dominates the mixed-phase behavior. In mixtures of anionic surfactant LAS with the AS sophorolipid, the globular micellar structure dominates over the entire composition and concentration range studied. In contrast, mixtures of LAS with the LS sophorolipid exhibit a rich evolution in phase behavior with solution composition and concentration. At low surfactant concentrations, the small unilamellar vesicle structure present for LS-rich solution compositions evolves into a globular micelle structure as the solution becomes richer in LAS. At higher surfactant concentrations, the disordered lamellar structure present for LS-rich compositions transforms to small vesicle/lamellar coexistence, to lamellar/micellar coexistence, to micellar/lamellar coexistence, and ultimately to a pure micellar phase as the solution becomes richer in LAS. The AS sophorolipid surfactant exhibits self-assembly properties similar to those of most other weakly ionic or nonionic surfactants that have relatively large headgroups. However, the more hydrophobic nature of the lactonic sophorolipid results in a more complex and unusual evolution in phase behavior with concentration and with concentration and composition when mixed with anionic surfactant LAS.

Rodlike complexes of a polyelectrolyte (hyaluronan) and a protein (lysozyme) observed by SANS.

We study by small-angle neutron scattering (SANS) the structure of hyaluronan -lysozyme complexes. Hyaluronan (HA) is a polysaccharide of 9 nm intrinsic persistence length that bears one negative charge per disaccharide monomer (M(mol) = 401.3 g/mol); two molecular weights, M(w) = 6000 and 500,000 Da were used. The pH was adjusted at 4.7 and 7.4 so that lysozyme has a global charge of +10 and +8, respectively. The lysozyme concentration was varied from 3 to 40 g/L at constant HA concentration (10 g/L). At low protein concentration, samples are monophasic, and SANS experiments reveal only fluctuations of concentration, although, at high protein concentration, clusters are observed by SANS in the dense phase of the diphasic samples. In between, close to the onset of the phase separation, a distinct original scattering is observed. It is characteristic of a rod-like shape, which could characterize "single" complexes involving one or a few polymer chains. For the large molecular weight (500,000), the rodlike rigid domains extend to much larger length scale than the persistence length of the HA chain alone in solution and the range of the SANS investigation. They can be described as a necklace of proteins attached along a backbone of diameter of one or a few HA chains. For the short chains (M(w) ≈ 6000), the rod length of the complexes is close to the chain contour length (∼ 15 nm).

Surface and solution properties of anionic/nonionic surfactant mixtures of alkylbenzene sulfonate and triethyleneglycol decyl ether.

The surface adsorption behavior and the solution microstructure of mixtures of the C(6) isomer of anionic surfactant sodium para-dodecyl benzene sulfonate, ABS, with nonionic surfactant monodecyl triethyleneglycol ether, C(10)E(3,) have been investigated using a combination of neutron reflectivity, NR, and small-angle neutron scattering, SANS. In solution, the mixing of C(10)E(3) and ABS results in the formation of small globular micelles over most of the composition range (100:0 to 20:80 ABS/C(10)E(3)). Planar aggregates (lamellar or unilamellar vesicles, ULV) are observed for solution compositions rich in the nonionic surfactant (>80 mol % nonionic). Prior to the transition to planar aggregates, the micelle aggregation number increases with increasing nonionic composition. The lamellar-phase region is preceded by a narrow range of composition over which mixtures of micelles and small unilamellar vesicles coexist. The variation in surface absorption behavior with solution composition shows a strong surface partitioning of the more surface-active component, C(10)E(3). This pronounced departure from ideal mixing is not readily explained by existing surfactant mixing theories. In the presence of Ca(2+) ions, a more complex evolution of solution phase behavior with solution composition is observed. The lamellar-phase region occurs over a broader range of solution compositions at the expense of the small-vesicle phase. The phase boundaries are shifted to lower nonionic compositions, and the extent to which the solution-phase diagrams are modified increases with increasing calcium ion concentration. The SANS data for the large planar aggregates are consistent with large polydisperse flexible unilamellar vesicles. In the presence of Ca(2+) ions, the surface adsorption patterns become more consistent with ideal mixing in the nonionic-rich region of the surface-phase diagram. However, in the ABS-rich regions the surface behavior is more complex because of the spontaneous formation of more complex surface microstructures (bilayers to multilayers). Both in water and in the presence of Ca(2+) ions the variations in the surface adsorption behavior and in the solution mesophase structure do not appear to be closely correlated.

Solution self-assembly and adsorption at the air-water interface of the monorhamnose and dirhamnose rhamnolipids and their mixtures.

The self-assembly in solution and adsorption at the air-water interface, measured by small-angle neutron scattering, SANS, and neutron reflectivity, NR, of the monorhamnose and dirhamnose rhamnolipids (R1, R2) and their mixtures, are discussed. The production of the deuterium-labeled rhamnolipids (required for the NR studies) from a Pseudomonas aeruginosa culture and their separation into the pure R1 and R2 components is described. At the air-water interface, R1 and R2 exhibit Langmuir-like adsorption isotherms, with saturated area/molecule values of about 60 and 75 Å(2), respectively. In R1/R2 mixtures, there is a strong partitioning of R1 to the surface and R2 competes less favorably because of the steric or packing constraints of the larger R2 dirhamnose headgroup. In dilute solution (<20 mM), R1 and R2 form small globular micelles, L(1), with aggregation numbers of about 50 and 30, respectively. At higher solution concentrations, R1 has a predominantly planar structure, L(α) (unilamellar, ULV, or bilamellar, BLV, vesicles) whereas R2 remains globular, with an aggregation number that increases with increasing surfactant concentration. For R1/R2 mixtures, solutions rich in R2 are predominantly micellar whereas solutions rich in R1 have a more planar structure. At an intermediate composition (60 to 80 mol % R1), there are mixed L(α)/L(1) and L(1)/L(α) regions. However, the higher preferred curvature associated with R2 tends to dominate the mixed R1/R2 microstructure and its associated phase behavior.

Mixing behavior of the biosurfactant, rhamnolipid, with a conventional anionic surfactant, sodium dodecyl benzene sulfonate.

The use of small angle neutron scattering, SANS, neutron reflectivity, NR, and surface tension to study the mixing properties of the biosurfactant rhamnolipid with a conventional anionic surfactant, sodium dodecyl 6-benzene sulfonate, LAS, is reported. The monorhamnose rhamnolipid, R1, mixes close to ideally with LAS at the air-water interface, whereas for mixtures of LAS with the dirhamnose rhamnolipid, R2, the LAS strongly partitions to the air-water interface relative to R2, probably because of the steric hindrance of the larger R2 headgroup. These trends in the binary mixtures are also reflected in the ternary R1/R2/LAS mixtures. However, for these ternary mixtures, there is also a pronounced synergy in the total adsorption, which reaches a maximum for a LAS/rhamnolipid mole ratio of about 0.6 and a R1/R2 mol ratio of about 0.5, an effect which is not observed in the binary mixtures. In solution, the R1/LAS mixtures form relatively small globular micelles, L(1), at low surfactant concentrations (<20 mM), more planar structures (lamellar, L(α), unilamellar/multilamellar vesicles, ulv/mlv) are formed at higher surfactant concentrations for R1 and LAS rich compositions, and a large mixed phase (L(α)/L(1) and L(1)/L(α)) region forms at intermediate surfactant compositions. In contrast, for the R2/LAS mixtures, the higher preferred curvature of R2 dominates the phase behavior. The predominant microstructure is in the form of small globular micelles, except for solution compositions rich in LAS (>80 mol % LAS) where more planar structures are formed. For the ternary mixtures, there is an evolution in the resulting phase behavior from one dominated by L(1) (R2 rich) to one dominated by planar structures, L(α), (R1, LAS rich), and which strongly depends upon the LAS/rhamnolipid and R1/R2 mole ratio.

Chain conformation: A key parameter driving clustering or dispersion in polyelectrolyte - Colloid systems.

The work presents the characterization of Pluronic F127 micellar solutions in presence of hyaluronic acid in semi-dilute regime. The effects of the nature and salt concentration are investigated by differential scanning calorimetry and small angle neutron scattering. Hyaluronic acid reduces the critical micellar temperature to the same extend as an increase of the ionic strength. Within the investigated HA concentration range, the size and shape of the micelles are not modified by the addition of HA but their dispersion state depends on the salt concentration. By increasing the ionic strength we observe the formation of small micellar clusters which organize into a face-centered cubic liquid crystalline phase at high salt concentration. This behavior is reinforced by increasing the HA concentration or molecular weight. The nature of the salt plays also a role and divalent cations such as Ca2+ promote the clustering of micelles and their crystallization. The origin of the aggregative behavior is the change of the HA chain conformation -from stretched to coil- by addition of salt which in turn induces an excluded volume around the micelles and exerts a depletion interaction.

Structural investigation of carbosilane liquid crystalline dendrimers.

X-ray and neutron scattering investigations have been made on two series of liquid crystal dendrimers. The low generations (first to fourth) predominantly show smectic phases. The fifth generation shows a tendency to form columnar phases and two different types have been observed. The transition from smectic to columnar has been explained in terms of the distance between the dendritic core and the mesogenic units. As the generation number is increased, the distance increases until it becomes greater than the maximum length of the flexible spacers causing a change in molecular shape and the formation of columnar phases. Although the materials are nearly monodisperse, the small variation in the number of mesogens per molecule gives rise to some subtle structural effects. Two coexisting structures have been observed over large temperature ranges in some materials and small angle neutron scattering indicates that there is some microphase segregation which is a reversible function of temperature.