Lα Phase Research Articles

Microfluidic SAXS Study of Lamellar and Multilamellar Vesicle Phases of Linear Sodium Alkylbenzenesulfonate Surfactant with Intrinsic Isomeric Distribution

The structure and flow behavior of a concentrated aqueous solution (45 wt %) of the ubiquitous linear sodium alkylbenzenesulfonate (NaLAS) surfactant is investigated by microfluidic small-angle X-ray scattering (SAXS) at 70 °C. NaLAS is an intrinsically complex mixture of over 20 surfactant molecules, presenting coexisting micellar (L1) and lamellar (Lα) phases. Novel microfluidic devices were fabricated to ensure pressure and thermal resistance, ability to handle viscous fluids, and low SAXS background. Polarized light optical microscopy showed that the NaLAS solution exhibits wall slip in microchannels, with velocity profiles approaching plug flow. Microfluidic SAXS demonstrated the structural spatial heterogeneity of the system with a characteristic length scale of 50 nL. Using a statistical flow-SAXS analysis, we identified the micellar phase and multiple coexisting lamellar phases with a continuous distribution of d spacings between 37.5 and 39.5 Å. Additionally, we showed that the orientation of NaLAS lamellar phases is strongly affected by a single microfluidic constriction. The bilayers align parallel to the velocity field upon entering a constriction and perpendicular to it upon exiting. On the other hand, multilamellar vesicle phases are not affected under the same flow conditions. Our results demonstrate that despite the compositional complexity inherent to NaLAS, microfluidic SAXS can rigorously elucidate its structure and flow response.

DOPC-DOPE composition dependent Lα-HII thermotropic phase transition: SAXD study

The structural polymorphism and parameters of lyotropic phases formed in the mixed dioleoylphosphatidylcholine-dioleoylphosphatidylethanolamine (DOPC-DOPE) system upon heating and varying DOPC:DOPE composition were studied by means of small-angle X-ray diffraction (SAXD). In the temperature range 5–80°C a sequence of fluid lamellar Lα – inverse hexagonal HII – inverse cubic QII phases was detected at DOPE mole fractions XDOPE≥0.65. A superposition of two bicontinuous cubic QII phases of Pn3m and Ia3d space groups was identified. The Lα to HII phase transition temperature, the onset of the QII phase formation, as well as the lattice spacings of the Lα and HII phases were found to decrease with rising DOPE content. Moreover, evidence of structural rearrangement during the Lα to HII phase transition is given and change of transition mechanism with varying XDOPE is suggested.

Vesicle Origami and the Influence of Cholesterol on Lipid Packing.

The artificial phospholipid Pad-PC-Pad was analyzed in 2D (monolayers at the air/water interface) and 3D (aqueous lipid dispersions) systems. In the gel phase, the two leaflets of a Pad-PC-Pad bilayer interdigitate completely, and the hydrophobic bilayer region has a thickness comparable to the length of a single phospholipid acyl chain. This leads to a stiff membrane with no spontaneous curvature. Forced into a vesicular structure, Pad-PC-Pad has faceted geometry, and in its extreme form, tetrahedral vesicles were found as predicted a decade ago. Above the main transition temperature, a noninterdigitated Lα phase with fluid chains has been observed. The addition of cholesterol leads to a slight decrease of the main transition temperature and a gradual decrease in the transition enthalpy until the transition vanishes at 40 mol % cholesterol in the mixture. Additionally, cholesterol pulls the chains apart, and a noninterdigitated gel phase is observed. In monolayers, cholesterol has an ordering effect on liquid-expanded phases and disorders condensed phases. The wavenumbers of the methylene stretching vibration indicate the formation of a liquid-ordered phase in mixtures with 40 mol % cholesterol.

Properties and ionic self-assembled structures from mixture of a bola-type strong alkali dication and a branched phosphoric acid

Ionic self-assembled structures have been prepared successfully between di-(2-ethylhexyl) phosphoric acid (DEHPA) and hexamethonium hydroxide (HMO(OH)2). The DEHPA/HMO(OH)2 complexes show good surface activity at a wide mixing molar ratio of DEHPA to HMO(OH)2 (ρ), within which the critical micellar concentration (cmc) is far below that of any single component. In bulk aqueous solutions, rich phase behavior was observed by varying cDEHPA and cHMO(OH)2. When the concentration of HMO(OH)2 is in the range of 10–100mmolL−1, isotropic L1 phases, birefringent Lα phases and a phase-separated region were successively observed with increasing cDEHPA. At high cHMO(OH)2 range (>78mmolL−1), a narrow L1/Lα two-phase region with the Lα phase at the bottom was noticed between the single L1 and single Lα phase regions. The rheological properties of the samples in the single Lα phase region at 2.6⩽ρ⩽2.8 are quite similar. Cryo-TEM and freeze-fracture TEM (FF-TEM) observations revealed the presence of multilamellar vesicles with flexible and even branched bilayers. At 2.2⩽ρ⩽2.6, however, the rheological properties are highly sensitive to ρ due to the sophisticated self-assembly behavior as proved by imaging studies and 2H NMR measurements. Closely-stacked flat structures which look like foams or cellular networks have been newly discovered. Interestingly, NaCl could arouse an L1 to Lα phase transition due to the suppression of the effective area of the hydrophilic headgroups of the ionic complexes, leading to an increase of the critical packing parameter p. The viscoelasticity properties of the salt-containing Lα phases decreased with increasing salinity. We hope our research can provide new ideas for the construction of supramolecular materials by surfactant ionic self-assembly (SISA) strategy.

Experimental and DFT studies on aggregation behavior of dodecylsulfonate-based surface active ionic liquids in water and ethylammonium nitrate

The present work aims to systematically study the aggregation behavior of one halogen-free surface active ionic liquid (SAIL), i.e., 1-butyl-3-methylimidazolum dodecylsulfonate ([C4mim][C12H25SO3]), in water and ethylammonium nitrate (EAN), respectively. Multiple-state ordered aggregates, viz. lyotropic liquid crystals (LLCs) (normal hexagonal and laminar lyotropic liquid phases, i.e. H1 and Lα phases) and lamellar gels, were facilely tuned only by the concentration of SAIL or solvent type. Furthermore, it is particularly interesting that LLC phases were constructed in H2O while lamellar gels were obtained in the EAN media environment, which were characterized by polarized optical microscopy (POM) and small-angle X-ray scattering (SAXS). According to the investigative SAXS patterns, some structural parameters were calculated, suggesting that a higher concentration of SAIL results in a denser arrangement whereas an opposite trend generates because of a higher temperature. FT-IR spectra and density functional theory (DFT) calculations reveal that both strong H-bonding and electrostatic interactions between EAN and the headgroups of [C4mim][C12H25SO3] facilitate gelation. For the self-assembled lamellar gels formed by [C4mim][C12H25SO3] in EAN, a thermally reversible sol–gel transition was observed by differential scanning calorimetry (DSC). The rheological results show that the H1 phase formed by [C4mim][C12H25SO3] in water exhibits a viscoelastic gel-like behavior among the whole frequency region while Lα phase displays a viscous behavior at lower frequencies and an elastic behavior at higher frequencies. This work is expected to set a basis for application of the eco-friendly halogen-free SAIL in some fields, e.g. electrochemistry, supramolecular chemistry and drug delivery.

Photopolymerization of Dienoyl Lipids Creates Planar Supported Poly(lipid) Membranes with Retained Fluidity.

Polymerization of substrate-supported bilayers composed of dienoylphosphatidylcholine (PC) lipids is known to greatly enhance their chemical and mechanical stability; however, the effects of polymerization on membrane fluidity have not been investigated. Here planar supported lipid bilayers (PSLBs) composed of dienoyl PCs on glass substrates were examined to assess the degree to which UV-initiated polymerization affects lateral lipid mobility. Fluorescence recovery after photobleaching (FRAP) was used to measure the diffusion coefficients (D) and mobile fractions of rhodamine-DOPE in unpolymerized and polymerized PSLBs composed of bis-sorbyl phosphatidylcholine (bis-SorbPC), mono-sorbyl-phosphatidylcholine (mono-SorbPC), bis-dienoyl-phosphatidylcholine (bis-DenPC), and mono-dienoyl phosphatidylcholine (mono-DenPC). Polymerization was performed in both the Lα and Lβ phase for each lipid. In all cases, polymerization reduced membrane fluidity; however, measurable lateral diffusion was retained which is attributed to a low degree of polymerization. The D values for sorbyl lipids were less than those of the denoyl lipids; this may be a consequence of the distal location of polymerizable group in the sorbyl lipids which may facilitate interleaflet bonding. The D values measured after polymerization were 0.1-0.8 of those measured before polymerization, a range that corresponds to fluidity intermediate between that of a Lα phase and a Lβ phase. This D range is comparable to ratios of D values reported for liquid-disordered (Ld) and liquid-ordered (Lo) lipid phases and indicates that the effect of UV polymerization on lateral diffusion in a dienoyl PSLB is similar to the transition from a Ld phase to a Lo phase. The partial retention of fluidity in UV-polymerized PSLBs, their enhanced stability, and the activity of incorporated transmembrane proteins and peptides is discussed.

Vitamin E Differentially Destabilizes Bilayer Structure of Docosahexaenoic and Oleic-Acid Containing Model Membranes

Vitamin E (α-tocopherol) is a lipid-soluble antioxidant that has a primary role of protecting polyunsaturated phospholipids from oxidation in membranes. Whether there is preferential interaction between α-tocopherol and polyunsaturated phospholipids to optimize this function has been a longstanding question. Here we compare the effect of α-tocopherol on the molecular organization of polyunsaturated 1-palmitoyl-2-docosahexaenoyl-sn-glycerophosphatidylethanolamine (16:0-22:6PE, PDPE) and monounsaturated 1-palmitoyl-2-oleoyl-sn-glycerophosphatidylethanolamine (16:0-18:1PE, POPE) in mixtures with sphingomyelin (SM). By solid-state 2H NMR spectroscopy, we directly observed POPE-d31 and PDPE-d31 (analogs of POPE and PDPE with a perdeuterated sn-1 chain) in the mixed membranes. In supplementary X-ray diffraction experiments, we further probed membrane architecture. At higher temperatures (>20 °C), the spectra observed for POPE-d31 in POPE/SM/α-tocopherol (2:2:1 mol) and for PDPE-d31 in PDPE/SM/α-tocopherol (2:2:1 mol) consist of a superposition of two spectral components that we ascribe to α-tocopherol promoting a transition from lamellar (Lα) to inverted hexagonal (HII) phase. This interpretation is confirmed by X-ray diffraction data. Analysis of depaked spectra shows that the amount of HII phase increases with temperature. The increase ranges from 7 to 28% between 31 and 55 °C for POPE-d31, while for PDPE-d31 the increase is less and ranges from 6 to 20% over the same temperature range. A more modest increase in acyl chain order is also seen for PDPE-d31 (3%) than POPE-d31 (8%) remaining in the Lα phase (37 °C). The molecular origin of the differential in bilayer stability between the two mixed membranes will be discussed in terms of the greater disorder of PDPE and its ability to accommodate α-tocopherol.

Activation Energy of the Low-pH-Induced Lamellar to Bicontinuous Cubic Phase Transition in Dioleoylphosphatidylserine/Monoolein.

Electrostatic interaction is an important factor for phase transitions between lamellar liquid-crystalline (Lα) and inverse bicontinuous cubic (QII) phases. We investigated the effect of temperature on the low-pH-induced Lα to double-diamond cubic (QII(D)) phase transition in dioleoylphosphatidylserine (DOPS)/monoolein (MO) using time-resolved small-angle X-ray scattering with a stopped-flow apparatus. Under all conditions of temperature and pH, the Lα phase was directly transformed into an intermediate inverse hexagonal (HII) phase, and subsequently the HII phase slowly converted to the QII(D) phase. We obtained the rate constants of the initial step (i.e., the Lα to HII phase transition) and of the second step (i.e., the HII to QII(D) phase transition) using the non-negative matrix factorization method. The rate constant of the initial step increased with temperature. By analyzing this result, we obtained the values of its apparent activation energy, Ea (Lα → HII), which did not change with temperature but increased with an increase in pH. In contrast, the rate constant of the second step decreased with temperature at pH 2.6, although it increased with temperature at pH 2.7 and 2.8. These results indicate that the value of Ea (HII → QII(D)) at pH 2.6 increased with temperature, but the values of Ea (HII → QII(D)) at pH 2.7 and 2.8 were constant with temperature. The values of Ea (HII → QII(D)) were smaller than those of Ea (Lα → HII) at the same pH. We analyzed these results using a modified quantitative theory on the activation energy of phase transitions of lipid membranes proposed initially by Squires et al. (Squires, A. M.; Conn, C. E.; Seddon, J. M.; Templer, R. H. Soft Matter 2009, 5, 4773). On the basis of these results, we discuss the mechanism of this phase transition.

Mixtures of Thermotropic Mesogens as Components of Model DPPC Membranes: Effects of Intermolecular Interactions on Phase Transitions

Thermotropic mesogens of different chemical nature - 4-pentyl-4′-cyanobiphenyl (5CB), azoxy nematic ZhK-440, and cholesteryl oleyl carbonate (COC) were introduced as dopants to hydrated DPPC, with their effects on phase transitions recorded by DSC. When mesogen pairs (5CB + ZhK-440 and 5CB + COC) were added at constant total concentration, dependence of transition temperature to Lα phase on 5CB concentration was linear for COC and nonlinear for ZhK-440, with effects of cyanobiphenyl-azoxybenzene charge transfer complexes manifested in both types of mesophases. Such dual doping of hydrated DPPC allows modeling of drug-membrane interactions in the case of joint application of different drugs.

Effects of Low Concentrations of Docosahexaenoic Acid on the Structure and Phase Behavior of Model Lipid Membranes.

In this paper we report an X-ray diffraction study on the phase behavior of binary lipid mixtures of 1-palmitoyl-2-docosahexaenoyl-sn-glycero-3-phosphoethanolamine (DHA-PE) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) at low concentrations below 5.0 mol% DHA-PE. Our results show that DHA-PE induces phase separation into a DHA rich liquid crystalline (Lα) phase and a DHA poor gel (Lβ′) phase at overall DHA-PE concentrations as low as 0.1 mol%. In addition, we find that the structure of the Lβ′ phase, from which the DHA-PE molecules are largely excluded, is modified in the phase-separated state at low DHA-PE concentrations, with a decrease in bilayer thickness of 1.34 nm for 0.1 mol% at room temperature, compared to pure DPPC bilayers. This result is contrary to that seen in similar studies on mono-unsaturated lipids where an increase in bilayer thickness is observed. The surprising effect of such low DHA-PE concentrations on membrane structure may be important in understanding the role of highly polyunsaturated lipids in biological membrane-based structures and similar artificial surfactant systems.

Phase Behavior of Commercial AES/Ethanol/H2O Ternary System

Phase behavior containing alkyl ethoxysulfates (AES), ethanol, and H2O over the whole concentration range was explored at 25°C. The system exhibited an isotropic solution phase (L), two different liquid crystalline phases: hexagonal phase (H), lamellar phase (Lα), and a biphasic region appearing with the ethanol concentration increasing. Polarized optical microscopy and small angle x-ray scattering were applied to characterize liquid crystalline phases. Direct two-phase titration and liquid chromatography–mass spectrometry (LC–MS) were employed to analyze the AES activity and homologues composition of the particles appearing in two-phase region.

Combination of MD Simulations with Two-State Kinetic Rate Modeling Elucidates the Chain Melting Transition of Phospholipid Bilayers for Different Hydration Levels.

The phase behavior of membrane lipids plays an important role in the formation of functional domains in biological membranes and crucially affects molecular transport through lipid layers, for instance, in the skin. We investigate the thermotropic chain melting transition from the ordered Lβ phase to the disordered Lα phase in membranes composed of dipalmitoylphosphatidylcholine (DPPC) by atomistic molecular dynamics simulations in which the membranes are subject to variable heating rates. We find that the transition is initiated by a localized nucleus and followed by the propagation of the phase boundary. A two-state kinetic rate model allows characterizing the transition state in terms of thermodynamic quantities such as transition state enthalpy and entropy. The extrapolated equilibrium melting temperature increases with reduced membrane hydration and thus in tendency reproduces the experimentally observed dependence on dehydrating osmotic stress.

Self-Assembly and Rheological Properties of a Pseudogemini Surfactant Formed in a Salt-Free Catanionic Surfactant Mixture in Water

The surface and bulk properties of bola-type dicarboxylic acid (sebacic acid, SA) and zwitterionic surfactant tetradecyldimethylamine oxide (C14DMAO) mixtures in aqueous solutions were studied. Surface tension measurements indicate a pronounced synergistic effect between SA and C14DMAO. In bulk aqueous solutions, rich phase behavior was observed with a varied SA-to-C14DMAO ratio (ρ) and a total surfactant concentration. Typically at ρ = 0.5, a novel pseudogemini surfactant (C14-S-C14) forms, driven by electrostatic interaction and hydrogen bonding. The C14-S-C14/H2O system exhibits rich phase behavior induced by the transition of aggregates. With increasing concentration of C14-S-C14, one can observe a viscous L1 phase, an L1/Lα two-phase region where a birefringent Lα phase is on the top of an L1 phase, a single Lα phase, and finally a mixture of an Lα phase and a precipitate. Microstructures formed in the Lα phases were determined by freeze-fracture transmission electron microscopy (FF-TEM) and cryogenic-transmission electron microscopy (cryo-TEM) observations. Polymorphic aggregation behavior was observed with the formation of a variety of bilayer structures including unilamellar vesicles, onions, and open and hyperbranched bilayers. Rheological measurements showed that the Lα phases are viscoelastic and sensitive to temperature where a quick loss of viscoelasticity was observed at elevated temperature.

Gelled Lyotropic Liquid Crystals

In our previous work we were able to prove that gelled bicontinuous microemulsions are a novel type of orthogonal self-assembled system. The study at hand aims at complementing our previous work by answering the question of whether gelled lyotropic liquid crystals are also orthogonal self-assembled systems. For this purpose we studied the same system, namely, water-n-decane/12-hydroxyoctadecanoic acid (12-HOA)-n-decyl tetraoxyethylene glycol ether (C10E4). The phase boundaries of the nongelled and the gelled lyotropic liquid crystals were determined visually and with (2)H NMR spectroscopy. Oscillating shear measurements revealed that the absolute values of the storage and loss moduli of the gelled liquid crystalline (LC) phases do not differ very much from those of the binary organogel. While both the phase behavior and the rheological properties of the LC phases support the hypothesis that gelled lyotropic liquid crystals are orthogonal self-assembled systems, freeze-fracture electron microscopy (FFEM) seems to indicate an influence of the gel network on the structure of the Lα phase and vice versa.

Fluorescence study of the effect of cholesterol on spectrin-aminophospholipid interactions.

The ability of the membrane skeletal protein spectrin to interact with phospholipids, and aminophospholipids in particular, in both natural and model membranes, is well documented. The present study involves phospholipid-induced quenching of tryptophan fluorescence to probe spectrin-membrane interactions in the presence and absence of cholesterol. We performed the experiments on small unilamellar vesicles of phospholipids made of DMPC and DMPC/DMPE and of DOPC and DOPC/DOPE with and without cholesterol at two different temperatures, one below at 15 °C and another above, at 50 °C, the main phase transition temperature (T m) of the bulk phospholipid. Results indicate that erythroid and brain spectrin binds DMPC/DMPE membranes by tenfold and 40-fold stronger, respectively, in the presence of 20 % cholesterol, up to which both gel (Lβ) and liquid crystalline (Lα) phases coexists, at 15 °C particularly in DMPC-based membranes containing saturated fatty acyl chains and not in DOPC-based membranes with appreciably lower T m. Time-resolved fluorescence and circular dichroism spectroscopic studies indicated no significant change in the mean lifetime of the tryptophan residues in spectrin and in the secondary structures of the proteins upon binding to the phospholipid SUVs.

Phase Coexistence in a Dynamic Phase Diagram.

Metastability and phase coexistence are important concepts in colloidal science. Typically, the phase diagram of colloidal systems is considered at the equilibrium without the presence of an external field. However, several studies have reported phase transition under mechanical deformation. The reason behind phase coexistence under shear flow is not fully understood. Here, multilamellar vesicle (MLV)-to-sponge (L3 ) and MLV-to-Lα transitions upon increasing temperature are detected using flow small-angle neutron scattering techniques. Coexistence of Lα and MLV phases at 40 °C under shear flow is detected by using flow NMR spectroscopy. The unusual rheological behavior observed by studying the lamellar phase of a non-ionic surfactant is explained using (2) H NMR and diffusion flow NMR spectroscopy with the coexistence of planar lamellar-multilamellar vesicles. Moreover, a dynamic phase diagram over a wide range of temperatures is proposed.

Unspecific membrane protein-lipid recognition: combination of AFM imaging, force spectroscopy, DSC and FRET measurements.

In this work, we will describe in quantitative terms the unspecific recognition between lactose permease (LacY) of Escherichia coli, a polytopic model membrane protein, and one of the main components of the inner membrane of this bacterium. Supported lipid bilayers of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoglycerol (POPG) (3:1, mol/mol) in the presence of Ca(2+) display lateral phase segregation that can be distinguished by atomic force microscopy (AFM) as well as force spectroscopy. LacY shows preference for fluid (Lα) phases when it is reconstituted in POPE : POPG (3:1, mol/mol) proteoliposomes at a lipid-to-protein ratio of 40. When the lipid-to-protein ratio is decreased down to 0.5, two domains can be distinguished by AFM. While the upper domain is formed by self-segregated units of LacY, the lower domain is constituted only by phospholipids in gel (Lβ) phase. On the one hand, classical differential scanning calorimetry (DSC) measurements evidenced the segregation of a population of phospholipids and point to the existence of a boundary region at the lipid-protein interface. On the other hand, Förster Resonance Energy Transfer (FRET) measurements in solution evidenced that POPE is selectively recognized by LacY. A binary pseudophase diagram of POPE : POPG built from AFM observations enables to calculate the composition of the fluid phase where LacY is inserted. These results are consistent with a model where POPE constitutes the main component of the lipid-LacY interface segregated from the fluid bulk phase where POPG predominates.

Amplitude-modulated atomic force microscopy reveals the near surface nanostructure of surfactant sponge (L(3)) and lamellar (L(α)) phases.

Amplitude-modulated atomic force microscopy (AM-AFM) has been used to study the nanostructure of cetylpyridinium chloride (CPCl)-hexanol-0.2 M NaCl sponge (L3) and lamellar (Lα) phases near a mica surface. For both phases, membrane volume fractions of 22, 27, and 32 vol % were investigated, with the L3 or Lα phase selected by adjusting the co-surfactant/surfactant ratio (hexanol/CPCl). For the L3 phase, the presence of the surface flattens the three-dimensional bulk structure. AM-AFM clearly resolves the membrane and solvent passages in the near surface layer. Increasing the membrane volume fraction decreases the size of the image features because of the lower solvent content. Within error, the average passage sizes in the near surface layer are the same as those in the bulk at the same concentration. Images of the Lα phase reveal undulating near surface sheets. At the highest membrane concentration, the image is very smooth, because the lamellar sheet is confined between the surface and the next near surface layer, which is in close proximity as a result of the low solvent content. As the membrane concentration is reduced, the space between layers is increased and undulations appear in the near surface lamellar structure. Undulations are more pronounced at the lowest membrane volume fraction.

Stimuli responsive polymorphism of C12NO/DOPE/DNA complexes: Effect of pH, temperature and composition

N,N-dimethyldodecylamine-N-oxide (C12NO) is a surfactant that may exist either in a neutral or cationic protonated form depending on the pH of aqueous solutions. Using small angle X-ray diffraction (SAXD) we observe the rich structural polymorphism of pH responsive complexes prepared due to DNA interaction with C12NO/dioleoylphosphatidylethanolamine (DOPE) vesicles and discuss it in view of utilizing the surfactant for the gene delivery vector of a pH sensitive system. In neutral solutions, the DNA uptake is low, and a lamellar Lα phase formed by C12NO/DOPE is prevailing in the complexes at 0.2≤C12NO/DOPE<0.6mol/mol. A maximum of ~30% of the total DNA volume in the sample is bound in a condensed lamellar phase LαC at C12NO/DOPE=1mol/mol and pH7.2. In acidic conditions, a condensed inverted hexagonal phase HIIC was observed at C12NO/DOPE=0.2mol/mol. Commensurate lattice parameters, aHC≈dLC, were detected at 0.3≤C12NO/DOPE≤0.4mol/mol and pH=4.9–6.4 suggesting that LαC and HIIC phases were epitaxially related. While at the same composition but pH~7, the mixture forms a cubic phase (Pn3m) when the complexes were heated to 80°C and cooled down to 20°C. Finally, a large portion of the surfactant (C12NO/DOPE>0.5) stabilizes the LαC phase in C12NO/DOPE/DNA complexes and the distance between DNA strands (dDNA) is modulated by the pH value. Both the composition and pH affect the DNA binding in the complexes reaching up to ~95% of the DNA total amount at acidic conditions.

Valinomycin-induced pore formation in thin lipid film and its effect on splay and bend elastic constant

AbstractValinomycin-induced rapid changes in the orientation patterns of lipid molecules under an applied field were observed in 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) thin films, aligned on polyvinyl-alcohol-coated indium tin oxide (ITO) glass electrodes both below (Lβ) and above (Lα) phase transition temperatures of DPPC. With the increasing concentration of valinomycin, Freedericksz's transition patterns change significantly. The values of splay (κ11) and bend (κ33) elastic constant changed by several orders of magnitude depending upon the concentration of valinomycin in the DPPC thin films. From the micrographs of field emission scanning electron microscopy, it was clear that pore formation on DPPC thin films would be a reason behind the decay of elastic constant. The decay of elastic constant was described by an exponential decay formula, y = A1e−x/t1+y0. From this point of view, we propose that our system can be used as a biosensor to detect antibiotic-like valinomycin.Keywords: valinomycinFreedericksz's transitionbiosensorlipid aggregatesmembrane elasticity AcknowledgementsThe helpful discussion with Dr Ashesh Nandy and Dr Smarajit Manna, Centre for Interdisciplinary Research and Education, and Dr Suman Bhandary, Bose Institute, are acknowledged.Disclosure statementNo potential conflict of interest was reported by the authors.Additional informationFundingWe thank Defense Research and Development Organization (DRDO), Defense Ministry, India, for their financial support [grant number: ERIP/ER/1103954/M/01/1413].