Critical Packing Parameter Research Articles

Additives-directed lyotropic liquid crystals architecture: Simulations and experiments

In this study, alkanes and sucrose esters are employed to investigate the influence of additives on lyotropic liquid crystal architecture. After molecular dynamic simulations and experiment characterization, we showed how the additives control the structure of LLCs. By controlling the polarity of additives, the phase behavior of LLCs can be engineered to form the required structure. Dissipative particle dynamics (DPD) is introduced for simulating the self-assembly of phytantriol (PT), providing intuitionistic images and structure information, which shows that additives with low-polarity complicate the internal structure of liquid crystal systems. Then the ternary phase diagrams of additives, PT, and water are constructed to systematically study the effects of additives on the phase behavior of LLCs. Consistent with DPD simulation results, there is a certain regularity in the effects of additives on the structure of liquid crystals. The difference in the structure of LLCs is due to the variability in the critical packing parameter (CPP) obtained by changing the polarity of additives. Our findings demonstrate that additives polarity is a key factor in LLCs structure, and may pave a promising avenue for novel LLCs development and translation, determining the self-assembly process and the resulting phase of LLCs.

Spacer length effect on the aggregation behaviours of gemini surfactants in EAN

As the symbol of gemini surfactants, the spacer group connects two surfactant monomers and plays an important role in the self-assembling of gemini surfactants. Recent attention has been paid to the effects of spacer nature and length in aqueous systems. In this study, the aggregation behaviours of quaternary ammonium gemini surfactants 12-s-12 with different spacer length (s = 2, 3, 4, 5, 6, 8, 10, 12) have been investigated in the protic ionic liquid EAN. The micellization behaviour was characterized by surface tension measurement. With the help of small-angle X-ray scattering (SAXS), the size and shape of aggregates were verified. The spacer length effect could be reflected by the changes in the micellization and phase behaviours of 12-s-12/EAN systems. The critical packing parameter of gemini molecules would decrease monotonically with the spacer length, which is supported by SAXS results. Due to the charge screening effect of EAN, the aggregation behaviours of 12-s-12 would be mainly influenced by spacer length. Our results would be the important supplement to the spacer length effect of gemini surfactants in the nonaqueous systems. With the increase of spacer chain length, the reverse hexagonal lyotropic liquid crystal phase would transform into the micellar phase.

Contrasting effect of 1-butanol and 1,4-butanediol on the triggered micellar self-assemblies of C16-type cationic surfactants.

The self-assembly in aqueous solutions of three quaternary salt-based C16-type cationic surfactants with different polar head groups and identical carbon alkyl chain viz., cetylpyridinium bromide (CPB), cetyltrimethylammonium tosylate (CTAT), and cetyltriphenylphosphonium bromide (CTPPB) in the presence of 1-butanol (BuOH) and 1,4-butanediol (BTD) was investigated using tensiometry, 2D-nuclear Overhauser enhancement spectroscopy (2D-NOESY) and small angle neutron scattering (SANS) techniques. The adsorption parameters and micellar characteristics evaluated at 303.15 K distinctly showed that BuOH promotes the mixed micelle formation while BTD interfered with the micellization phenomenon. The SANS data fitted using an ellipsoid (as derived by Hayter and Penfold using the Ornstein-Zernike equation and the mean spherical approximation) and wormlike micellar models offered an insight into the micelle size/shape and aggregation number (Nagg) in the examined systems. The evaluated descriptors presented a clear indication of the morphology transition in cationic micelles as induced by the addition of the two alcohols. We also offer an investigation into the acceptable molecular interactions governing the differences in micelle morphologies, using the non-invasive 2D-NOESY technique and molecular modeling. The experimental observations elucidated from computational simulation add novelty to this work. Giving an account to the structural complexity in the three cationic surfactants, the molecular dynamics (MD) simulation was performed for CPB micelles in an aqueous solution of alcohols that highlighted the micelle solvation and structural transition, which is further complemented in terms of critical packing parameter (PP) for the examined systems.

Effects of unsaturated double bonds on adsorption and aggregation behaviors of amide-based cationic Gemini surfactants

Four cationic amide Gemini surfactants, containing unsaturated and saturated hydrophobic chains, were synthesized from oleamide propyl dimethylamine (PKO-18:1) and stearate amide propyl dimethylamine(PKO-18). The chemical structures of the synthesized compounds were characterized by FT-IR spectra and 1H NMR. The Krafft temperatures were experimentally determined.. Their critical micelle concentration(CMC) in the aqueous solutions were determined by surface tension and conductivity methods. Equilibrium surface tension parameters such as γcmc, pC20, Гmax, Amin, △G°mic(Gibbs free energy of micellization), △G°ads(Gibbs free energy of adsorption) were obtained. Their adsorption behavior was analyzed through dynamic surface tension. Also, their self-assembly behaviors were investigated by negative-stained transmission electron microscopy(TEM) and critical packing parameter calculation. The results showed that the unsaturated double bond in hydrophobic chains was favorable for lowering the Krafft temperature and CMC. The oleamide-based Gemini surfactants present a lower Krafft temperature, higher surface activity and the adsorption kinetic process were conformed mixed diffusion-kinetic control model. The TEM results showed that the oleamide-based Gemini surfactants containing unsaturated double bonds in hydrophobic chains preferentially form worm-like micelles in solution. However, the stearate amide Gemini surfactants whose hydrophobic chains are saturated alkyl chains tend to form spherical aggregates in solution.

Highly Sustainable and Completely Amorphous Hierarchical Ceramide Microcapsules for Potential Epidermal Barrier

As a main component of the stratum corneum, ceramides can construct protective lamellae to provide an epidermal barrier against dehydration or external microorganisms. However, as ceramide molecules can easily form the isolated crystalline phase through self-assembly due to the amphipathic nature of bioactive lipids, the effective incorporation of ceramides into liquid media is the remaining issue for controlled release. Here, we report an unprecedented effective strategy to fabricate a completely amorphous and highly sustainable hierarchical ceramide polymer microcapsule for promising epidermal barrier by using the interpenetrating and cooperative self-construction of conical amphiphiles with a different critical packing parameter. The self-constructed amorphous architecture of ceramides in polymer microcapsule is achieved by the facile doping of conical amphiphiles and subsequent in situ polymerization of shell polymer in the core-shell geometry. It is experimentally revealed that an irregular cooperative packing structure formed by adaptive hydrophobic–hydrophilic interactions of cylindrical ceramides and conical amphiphiles in the confined microcapsule geometry enables a completely amorphous morphology of ceramides to be realized during the spontaneous encapsulation process. Furthermore, this elegant approach affords a highly dispersible and uniform hierarchical amorphous ceramide microcapsule with a greatly enhanced long-term stability compared to conventional crystalline ceramides.

Synthesis and Properties of Amide Gemini Surfactants

Abstract In the present study, three amide Gemini surfactants of different chain lengths were synthesized, namely N,N-bis-dodecyl-2,6-pyridinium dimethylamide propionate sodium (DLP-12), N,N-bis-tetradecyl-2,6-pyridinium dimethylamide propionate sodium (DLP-14) and N,N-bis-hexadecyl-2,6-pyridinium dimethylamide propionate sodium (DLP-16). Their chemical compositions and structures were characterized by FTIR, 1H NMR and mass spectrometry. Moreover, tensiometry, Langmuir monolayer and conductivity measurements were performed to investigate the micellization and chemical surface properties of the surfactants. The results of the characterization proved that the synthesis of DLP-12, DLP-14 and DLP-16 was successful. Among the investigated surfactants DLP-16 had optimum properties such as a higher emulsification ability as well as a lower surface tension. Furthermore, by calculating the critical packing parameter (CPP), the aggregation morphology of the DLP-12, DLP-14 and DLP-16 was also predicated in this study.

Rhamnolipids biosurfactants as potential modulators of phase and partitioning behavior in micellar systems of aliphatic alcohol ethoxylate surfactants

Abstract The impact of rhamnolipids (RL) biosurfactants presence on the phase-separation equilibrium, micellar properties and partitioning behavior of systems containing the aliphatic non-ionic surfactant Tergitol 15-S-7 (Tg7) was studied in this work. The cloud points of Tg7 solutions (1‐ 10% w/w) in water and sodium citrate (NaCit) buffers pH 7.00 were increased after the RL addition (0.25% w/w) while they were decreased in NaCit pH 5.00. The most marked changes were verified for those systems with low Tg7 concentrations ( 7°). As expected, the zeta potential (ζ) of non-ionic Tg7 systems was close to zero; however, ζ became clearly negative (≅ −20 mV) in NaCit pH 7.00 after the addition of RL. This finding suggested that RL, which is negatively charged at pH 7.00, self-incorporated into Tg7 micelles and conferred them its charge. Hydrodynamic diameter (Dh) was either increased (in citrate media) or decreased (in water) by the RL, depending on the changes caused in the critical packing parameter of mixed micelles. Interestingly, an exponential decay equation, useful for predictive purpose, was found to correlate the cloud point with the hydrodynamic diameter, thus evidencing the crucial role of micelle size/shape on the phase separation. The partitioning behavior of cibacron blue (CB) and malaquite green (MG), negatively and positively charged dyes respectively, in Tg7 aqueous micellar two-phase systems (AMTPS) was significantly affected by the RL 0.25% w/w. In AMTPS with pH 7.00, the RL induced opposite effects, either duplicating the partition coefficient of MG or reducing it to a half for CB. Attractive and repulsive electrostatic interactions between the negatively charged mixed micelles and the partitioned molecules would be responsible of these trends. These results demonstrate the role of RL as a modulator of partitioning behavior of charged molecules and its potential use to improve recoveries and selectivity in a purification protocol.

Dynamic Collapse Mechanism of Alveolar Type 1 Caveolae Buds Modeled as Cubic Mesophase Lyotropic Liquid Crystal Formation and Growth

The alveolar type 1 (AT1) cells cover 95% of the cell surface area while the alveolar type 2 cells cover the remaining 5% of 100–150 m2 surface area of the lung. AT1 maintain membrane integrity by surface tension via caveolin proteins that stretch and collapse the membrane bilayer in physiological pressure cycling, however, collapse mechanics of the AT1 membrane have not been elucidated. Golani et al. modeled globular caveolin collapse structure base on mean curvature and lateral tension, and other sources have constructed similar models. The parameters are transformations of the critical packing parameter CPP equals monomer dimensions predicts that the monolayer shape of surfactants, described as v/al. Deng et al. model for gemini surfactants at the air‐water interface and Turner et al. model for the formation of caveolae bulbs via energy displacement of a membrane bound proteins have proposed similar geometric theories that show resemblance to lyotropic liquid crystal swell equation. The models feature common mathematical properties which are 1) spherical geometry, 2) lattice parameter‐based expansion, and 3) monomer population as mechanical descriptors of bilayer transformation. Each model correlated positively with cubic formation and decrease in surface tension. Krianeva et al. showed that monolayer of monoolein formed a new phase of bicontinuous phase, P4332, as the concentration of protein Horse cytochrome c increased. The spherical formation models predicted mesophases are cubic meaning that they are CPP >> 1, micellar cubic shape. The overall result, the caveolin bud shape is cubic bicontinuous mesophase, which is stabilized under physiological pressure cycling in the AT1 cell. We propose, the caveolin bud shape is a cubic bicontinuous mesophase stabilized under physiological pressure cycling in AT1 cell membrane and mechanics can be modeled by using the lamellar to cubic transition or the swelling law using change in surface tension vs lattice parameter as the formation rate. Furthermore, caveolin and cavin proteins present during the time of formation induce invagination, and, second, stabilization and fragility. Agarwal et al. show the transition phase between isotropic and cubic mesophase is a volume fraction difference of 0.05, a metastable polyhedral lattice produced by caveolin proteins, characterizing bud formation as plastic liquid crystal phase transition. This model could explain mechanoprotection by caveolae bud, and gives us a platform to think about self‐assembling monomer‐based medicines when approaching physical stretch dysfunction repair in the lung.Equations are models that describe cubic expansion from the lamellar setting across several membrane simulations. Equation 1 (left) describes the radius, r1, of Gemini surfactant. Equation 2 (middle) describes the formation of caveolae bulbs via the energy displacement of membrane‐bound proteins. Equation 3 (left) describes the swelling law of lyotropic mesophases.Figure 1

Modification of lecithin-based emulsions with phospholipases

ABSTRACT Phospholipases have been used in different food processes, but mainly on degumming vegetable oils. More recently, the use of these enzymes has been extended to the manufacture of bread and dairy products. However, little is known on phospholipases effect on lecithin-based emulsions and how the emulsion size contributes to such effect. This work aimed to explore the effect of phospholipase type A1 (PLA1) on lecithin-based emulsions with different droplet size distribution. The PLA1 was able to hydrolyze lecithin phospholipids aggregated in (oil-in-water) emulsions, generating different lysophospholipids. The larger the particle size in the emulsion, the higher the enzymatic activity of PLA1. According to theoretical calculations, the lysophospholipids had higher hydrophile-lipophile balance (HLB) and had a lower critical packing parameter (p) than phospholipids. In consequence, the emulsions having more lysophospholipids were more prone to flocculate and to coalescence.

Phase inversion characteristics observed upon water dilution of a bidiscontinuous phase

This study presents a directly aggregated pseudo-ternary system. The three apexes of the investigated system represent a surfactant phase [Tween 80:propylene glycol (9:1 wt ratio)], an oil phase [isopropyl myristate:benzyl alcohol (7.5:2.5 wt ratio)], and water. Within the pseudo-ternary system, water dilution line, termed N91 (90 wt% surfactant phase and 10 wt% oil phase), was found to represent transparent and thermodynamically stable compositions from concentrate to high water dilution (>95 wt% water). Despite that the system was found to be directly aggregated, dilution line N91 exhibited classical L2→L1 phase inversion characteristics (at 39 wt% water). To explain this phenomenon, a novel structural interpretation regarding the observed inversion as an obstruction of the bidiscontinuous phase, consisting of oil and water-segregated domains, is proposed. The evaluation of dilution line N91 was based on electrical conductivity, SAXS, SD-NMR, rheometry, DSC and cryo-TEM.The structural transitions along water dilution line N91 were found to be as follows: 'pseudo L1' (pseudo direct surfactant-oil aggregates) → bi-discontinuous structure (of which partial is a hexagonal H1 mesophase) → L1.We concluded that the high concentration of low CPP (critical packing parameter) surfactant plays a major role in determining the system's geometry throughout the water dilution line. As a result, the proposed interpretation of the structural inversion observed along dilution line N91 differs from the classical U-type inversion interpretation (L2 →bicontinuous →L1).

Block copolymer vesicles via liquid/liquid interface-mediated self-assembly

Self-assembly behavior of amphiphilic block copolymers has attracted much attention recently. In this paper, a novel liquid/liquid interface-mediated self-assembly behavior of block copolymer is reported. An aqueous solution of HAuCl4 and a chloroform solution of poly(2-vinylpyridine)-block-polycaprolactone (P2VP199-b-PCL22) are employed as the upper phase and the bottom phase, respectively. Structural transitions from toroids and plate like structures to vesicles and large compound vesicles are observed in the bottom phase by using transmission electron microscopy (TEM). It is proved that vesicles and large compound vesicles are formed through adsorption and desorption of copolymers at the liquid/liquid interface, molecular aggregation and microphase separation in the bottom phase due to the amphiphilic property of protonated P2VP199-b-PCL22. The well-dispersed Au nanoparticles are formed during the self-assembly process and embedded in the bilayers of the vesicles. The concentrations of HAuCl4 and P2VP199-b-PCL22 have an effect on the self-assembly behavior. A unique structure, “pearl necklace”, is obtained at higher concentrations. In addition, it was found that P2VP252-b-PCL44 also formed vesicles, while P2VP195-b-PCL75 and P2VP195-b-PCL307 formed spherical micelles in the bottom phase through the same approach. The dependence of the aggregate morphology and the molecular structure was discussed based on the critical packing parameter, p.

Synthesis and biological activity of analogs of the antifungal antibiotic UK-2A. III. Impact of modifications to the macrocycle isobutyryl ester position.

Fenpicoxamid (Inatreq™ active), a new fungicide under development by Corteva Agriscience™, Agriculture Division of DowDuPont, is an isobutyryl acetal derivative of the antifungal antibiotic UK-2A. SAR studies around the picolinamide ring and benzyl substituents attached at positions 3 and 8, respectively, of the UK-2A bislactone macrocycle have recently been documented. This study focuses on replacement of the isobutyryl ester group in the 7 position. Thirty analogs, predominantly esters and ethers, were prepared and evaluated for inhibition of mitochondrial electron transport and in vitro growth of Zymoseptoria tritici, Leptosphaeria nodorum, Pyricularia oryzae and Ustilago maydis. Aliphatic substituents containing four to six carbon atoms deliver strong intrinsic activity, the pivaloate ester (IC50 1.44 nM) and the n-butyl, 1-Me-propyl, 3,3-diMe-propyl and 2-c-propyl propyl ethers (IC50 values = 1.08, 1.14, 1.15 & 1.32 nM, respectively) being the most active derivatives. QSAR modelling identified solvation energy (Esolv ) and critical packing parameters (vsurf_CP) as highly significant molecular descriptors for explaining relative intrinsic activity of analogs. Activity translation to fungal growth inhibition and disease control testing was significantly influenced by intrinsic activity and physical properties, the cyclopropanecarboxylate ester (log D 3.67, IC50 3.36 nM, Z. tritici EC50 12 μg L-1 ) showing the strongest Z. tritici activity in protectant tests. Substitution of the isobutyryl ester group of UK-2A generates analogs that retain strong antifungal activity against Z. tritici and other fungi. © 2019 Society of Chemical Industry.

Luminescent Vesicles and Lyotropic Liquid Crystals in Ethylammonium Nitrate from a Partially Amphiphilic Eu Complex.

Soft luminescent materials have attracted much attention because of their self-assembled and controllable properties. To explore their facile and effective fabrication ways, we report here the self-assembling of luminescent vesicles and lyotropic liquid crystals (LLCs) in a protic ionic liquid, ethylammonium nitrate, by a partially amphiphilic europium β-diketonate complex (Eu(III)) with a 1-dodecyl-3-methylimidazolium cation as the counter ion. An interesting result came from the complex-induced vesicle formation of corresponding amphiphile, 1-dodecyl-3-methylimidazolium bromide ([C12mim]Br), which has been rarely reported in the past. It was the interaction between the Eu(III) and imidazolium group that changed the critical packing parameter of [C12mim]Br, which finally resulted in the occurrence of vesicles. The obtained vesicle aggregates exhibited enhanced fluorescence intensity and lifetime compared to those of Eu(III) solution. Meanwhile, a hexagonal LLC phase with better fluorescence properties was found at higher [C12mim]Br concentration. The obtained photophysical data confirmed that the order degree of Eu(III)-containing aggregates could effectively increase the energy transition efficiency of ligands. The better luminescent properties of LLC resulted from the stronger stabilizing and binding effects on Eu(III) in LLC than that in vesicles, which might be caused by closer molecular packing in LLC. The results presented here will not only expand the strategy of constructing lanthanide-containing luminescent soft materials in ionic liquids but also provide reference to better understand the effect of organized aggregates on luminescence properties.

Rapid Stabilization of Immiscible Fluids using Nanostructured Interfaces via Surfactant Association.

Surfactant molecules have been extensively used as emulsifying agents to stabilize immiscible fluids. Droplet stability has been shown to be increased when ordered nanoscale phases form at the interface of the two fluids due to surfactant association. Here, we report on using mixtures of a cationic surfactant and long chained alkenes with polar head groups [e.g., cetylpyridinium chloride (CPCl) and oleic acid] to create an ordered nanoscale lamellar morphology at aqueous-oil interfaces. The self-assembled nanostructure at the liquid-liquid interface was characterized using small-angle x-ray scattering, and the mechanical properties were measured using interfacial rheology. We hypothesize that the resulting lamellar morphology at the liquid-liquid interface is driven by the change in critical packing parameter when the CPCl molecules are diluted by the presence of the long chain alkenes with polar head groups, which leads to a spherical micelle-to-lamellar phase transition. The work presented here has larger implications for using nanostructured interfacial material to separate different fluids in flowing conditions for biosystems and in 3D printing technology.

Aggregation Behavior and Antioxidant Properties of Amphiphilic Fullerene C60 Derivatives Cofunctionalized with Cationic and Nonionic Hydrophilic Groups.

Amphiphilic derivatives of fullerene C60 are attractive from viewpoints of supramolecular chemistry and biomedicine. The establishment of relationships among the molecular structure, aggregation behavior and properties such as scavenging radicals of the amphiphilic C60 derivatives is the key to push these carbon nanomaterials to real applications. In this work, six monosubstituted C60 derivatives were synthesized by a one-step quaternization of their neutral precursors, which bear Percec monodendrons terminated with oligo(poly(ethylene oxide)) (o-PEO) chain(s). The main difference among the C60 derivatives lies in the number and substituted position of the o-PEO chain(s) within the Percec monodendron. Derivative with a 4-substitution of the o-PEO chain still showed limited solubility in water. Other derivatives possessing two or three o-PEO chains exhibited much improved solubilities and rich aggregation behavior in water. It was found that the formation of aggregates is regulated both by the number and the substituted pattern of the o-PEO chains. Typical morphologies include nanosheets, nanowires, vesicles, nanotubes, and nanorods. Although the structures of the C60 derivatives are different from those of traditional surfactants, their aggregation behavior can be also well explained by applying the theory of critical packing parameter. Interestingly, the capabilities of the C60 derivatives to scavenge the hydroxyl radicals (OH·-) followed the same order of their solubility in water, where the compound bearing three o-PEO chains with a 2,3,4-substitution got the champion quenching efficiency of ∼97.79% at a concentration of 0.15 mg·mL-1 (∼0.11 mmol·L-1).

Synthesis and viscoelastic properties of gemini surfactants containing redox-active ferrocenyl groups

A type of electro-responsive threadlike micelle (TLM) was formed using new cationic gemini surfactants Fc11-n-11Fc with redox-active ferrocenyl groups in the gemini alkyl chains. By varying the alkyl spacer length, we synthesized several kinds of Fc11-n-11Fc-based gemini surfactants with n = 3, 4, 6, and characterized their viscoelastic behavior, surface activity, and redox properties in aqueous solutions through the use of oscillatory rheology, surface tensiometry, cyclic voltammetry, and UV–vis spectroscopic measurements. The Fc11-4-11Fc solution was found to form highly viscous (˜103 Pa⋅s) TLMs. Unlike the monomeric surfactant, the Fc11-4-11Fc micellar solution maintained its high viscosity even after adding extra builder and/or electrolyte agents. The surface-tensiometric measurements indicate that the effective molecular area of Fc11-n-11Fc at the air/water interface systematically increased with the alkyl spacer length. Using the critical packing parameters estimated with the molecular area, Fc11-4-11Fc is expected to be the most suitable for rod-like micellar growth. Importantly, the viscosity of Fc11-4-11Fc micellar solution could be decreased to that of pure water as a response to electrochemical oxidation reaction, and recovered by the subsequent re-reduction reaction. Hence, the gemini surfactants prepared in this study are a promising class of candidates for potential smart soft material applications.

Water-in-CO2 Microemulsions Stabilized by Fluorinated Cation-Anion Surfactant Pairs.

High-water-content water-in-supercritical CO2 (W/CO2) microemulsions are considered to be green, universal solvents, having both polar and nonpolar domains. Unfortunately, these systems generally require environmentally unacceptable stabilizers like long and/or multifluorocarbon-tail surfactants. Here, a series of catanionic surfactants having more environmentally friendly fluorinated C4-C6 tails have been studied in terms of interfacial properties, aggregation behavior, and solubilizing power in water and/or CO2. Surface tensions and critical micelle concentrations of these catanionic surfactants are, respectively, lowered by ∼9 mN/m and 100 times than those of the constituent single fluorocarbon-tail surfactants. Disklike micelles in water were observed above the respective critical micelle concentrations, implying the catanionic surfactants have a high critical packing parameter, which should be suitable for the formation of reverse micelles. Based on visual observation of phase behavior and Fourier transform infrared spectroscopic and small-angle neutron scattering studies, one of the three catanionic surfactants tested was found to form transparent single-phase W/CO2 microemulsions with a water-to-surfactant molar ratio of up to ∼50. This is the first successful demonstration of the formation of W/CO2 microemulsions by synergistic ion-pairing of anionic and cationic single-tail surfactants. This indicates that catanionic surfactants offer a promising approach to generate high-water-content W/CO2 microemulsions.

Temperature-responsive self-assembled nanostructures from lysine-based surfactants with high chain length asymmetry: from tubules and helical ribbons to micelles and vesicles.

Stimuli-sensitive self-assembled nanostructures are of great relevance for the templating of nanomaterials and the design of efficient systems for the controlled delivery of molecules. Amino acid-based surfactants often display such fascinating self-assembly due to a combination of molecular features such as critical packing parameter, chirality and H-bonding interactions. Herein, we focus on a family of newly synthesized double-chained alkylcarboxylates derived from l-lysine, and designated by 8Lysn, mLys8, with n, m = 12, 14 and 16, and 12Lys16 and 16Lys12, where the numbers represent the number of C atoms in each hydrocarbon chain. The effects of the chain length asymmetry and structural isomerism of the surfactants on their interfacial properties, thermal behavior and self-assembly in water were investigated by a comprehensive toolbox, including surface tension, DSC, imaging (light microscopy, SEM, TEM and AFM) and SAXS. All the surfactants below their Krafft temperature self-organize into tubular structures of various morphologies (flat structures, twisted and coiled ribbons and hollow tubes), forming hydrogels at low surfactant concentration. Upon the solubilization phase transition, micelles or vesicles are formed depending on the surfactant structure, and the tubule-micelle or tubule-vesicle transition is thermoreversible. A molecular-level rationalization of the observed self-assembly and phase transition features is put forth.

Calculating the 'chain splay' of amphiphilic molecules: Towards quantifying the molecular shapes.

We report the first method to calculate a very important molecular level parameter of amphiphilic molecules- the 'chain splay'. The calculations employed a truncated cone geometry, as it is the most probable configuration adopted by various amphiphiles. This approach utilized known parameters including lipid length, cross-sectional area at the head group and molecular volume. This new parameter, i.e. the area at the chain end, perceived to be more sensitive than Israelachvili's famous shape factor or critical packing parameter (CPP). With relevant calculations, we demonstrate the fundamental roles of 'chain splay' to: a) reveal the critical contribution of molecular structure on average molecular shape and consequent self-assemblies, b) track the finest changes in molecular shapes within different bicontinuous cubic phases, c) obtain non-zero areas at the chain ends of amphiphiles that form normal (type 1) phases, d) back-calculate molecular volumes close to theoretical values, and e) find the link between molecular shapes and global curvatures of self-assemblies. This powerful feature advances our abilities towards quantitative estimation of spatial configurations adopted by amphiphilic molecules; moreover, it has a strong impact on predicting biomembrane structuring and nanoscale design of corresponding self-assemblies for a range of emerging applications.

Bile Salts Caught in the Act: From Emulsification to Nanostructural Reorganization of Lipid Self-Assemblies.

Bile salts (BSs) are important for the digestion and absorption of fats and fat-soluble vitamins in the small intestine. In this work, we scrutinized, with small-angle X-ray scattering (SAXS), the crucial functions of bile salts beyond their capacity for the interfacial stabilization of submicrometer-sized lipid particles. By studying a wide compositional range of BS-lipid dispersions using two widely applied lipids for drug-delivery systems (one a monoglyceride being stabilizer-sensitive and the other an aliphatic alcohol being relatively stabilizer-insensitive), we identified the necessary BS to lipid ratios to guarantee full emulsification. A novel ad hoc developed global small-angle-X-ray scattering analysis method revealed that the addition of BS hardly changes the bilayer thicknesses in bicontinuous phases, while significant membrane thinning is observed in the coexisting fluid lamellar phase. Furthermore, we show that a BS strongly decreases the average critical packing parameter. At increasing BS concentration, the order of phases formed is (i) the bicontinuous diamond cubic ( Pn3 m), (ii) the bicontinuous primitive cubic ( Im3 m), and (iii) the fluid lamellar phase ( Lα). These distinctive findings on BS-driven "emulsification" and "membrane curvature reduction" provide new molecular-scale insights for the understanding of the interfacial action of bile salts on lipid assemblies.