Distortion of the lamellar arrangement of phospholipids by deep rough mutant lipopolysaccharide from <Emphasis Type="Italic">Salmonella minnesota</Emphasis>

Summary The concentration dependent effects of deep rough mutant lipopolysaccharide (LPS) from Salmonella minnesota (R595) on two different phospholipid model membranes was investigated by differential scanning calorimetry and small-angle X-ray scattering (SAXS). At low concentrations of LPS the well ordered multilamellar arrangement of dipalmitoylphosphatidylcholine (DPPC) vesicles is strongly distorted resulting in a loss of positional correlation of the lipid lamellae and smaller domain sizes within the lamellae. The pre-transition of DPPC was abolished at a LPS/DPPC molar ratio of 0.1:1 and the main or chain melting transition was strongly broadened. Moreover, the enthalpy was significantly decreased and a transition was hardly detected at an equimolar mixture of LPS/DPPC. LPS also affected the lamellar arrangement of a mixture of dipalmitoylphosphatidylethanolamine (DPPE) and dipalmitoylphosphatidylglycerol (DPPG). Furthermore, a phase separation was observed for this phospholipid mixture resulting in DPPE enriched and depleted domains. Similarly to DPPC, only a weak phase transition was observed at the highest LPS concentration used (LPS/DPPE-DPPG 1:1 mol/mol). SAXS measurements showed that for both systems increasing the concentration of LPS resulted in a concomitant increase of the formation of cubic structures, which are predominant at an equimolar mixture of LPS/phospholipid. However, because of the small number of peaks it was not possible to unambiguously identify the space group of the cubic structure, complicated by the coexistence with a lamellar phase, which was particularly detectable for the LPS/DPPC mixture.     

Mixed layers of DPPC and a linear poly(ethylene glycol)-b-hyperbranched poly(glycerol) block copolymer having a cholesteryl end group

Interactions of the phospholipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) with the amphiphilic diblock copolymer Ch-lPEG₃₀-b-hbPG₂₄ (ChP) are studied at the air–water interface by surface pressure–mean molecular area (π–mmA) measurements of mixed Langmuir films and adsorption measurements of ChP to the air–water interface covered with DPPC monolayers at different initial surface pressure values π ₀. ChP is composed of a single hydrophobic cholesteryl (Ch) moiety covalently bound to a diblock copolymer consisting of a hydrophilic linear poly(ethylene glycol) (lPEG) block and a hydrophilic hyperbranched poly(glycerol) (hbPG) block. Langmuir isotherms and compression moduli of the mixed Langmuir films of different molar ratios reveal distinct interactions between DPPC and ChP during compression. It is demonstrated that the behavior of the DPPC/ChP mixtures is dominated by DPPC up to a molar ratio of 10:1, whereas the behavior is predominantly governed by ChP in mixtures with lower DPPC content (molar ratios of 5:1, 2:1, and 1:1). In adsorption measurements, a strong affinity of ChP to DPPC is observed after injection into the water subphase. The surface pressure value π _in up to which ChP is able to penetrate into DPPC monolayers is determined to the remarkably high value of 48.2 mN/m which attests the favorable interactions between DPPC and the Ch moiety of ChP. Atomic force microscopy on LB films of DPPC/ChP mixtures of different molar ratios transferred onto hydrophilic substrates confirms the presence of two different phases, a DPPC-rich phase and a ChP-rich phase.     

Excess molar enthalpies of the ternary system <Emphasis Type="Italic">p</Emphasis>-xylene+decane+diethyl carbonate

Excess molar enthalpies of the ternary system {x ₁ p-xylene+x ₂decane+(1–x ₁–x ₂)diethyl carbonate} and the involved binary mixtures {p-xylene+(1–x)decane}, {xp-xylene+(1–x)diethyl carbonate} and {xdecane+(1–x)diethyl carbonate} have been determined at the temperature of 298.15 K and atmospheric pressure, over the whole composition range, using a Calvet microcalorimeter. The experimental excess molar enthalpies H _m ^E are positive for all the binary systems studied over the whole composition range. Excess molar enthalpy for the ternary system is positive as well, showing maximum values at x ₁=0, x ₂=0.4920, x ₃=0.5080, H _m,123 ^E=1524 J mol^–1.     

Non-debye nature in thermal relaxation and thermal properties of lithium borate glasses studied by modulated DSC

Complex heat capacity, C _p ^*=C _p ^'–iC _p ^', of lithium borate glasses xLi₂O·(1–x)B₂O₃ (molar fraction x=0.00–0.30) has been investigated by Modulated DSC. We have analyzed the shape of C _p ^* by the Cole-Cole plot, performed fitting by the Havriliak-Negami equation, and then determined the parameters related to the non-Debye nature of thermal relaxation. Moreover, the concentration dependence of the thermal properties has been investigated. Glass transition temperatures become higher with the increase of molar fraction of Li₂O and shows the board peak around x=0.26. Temperature ranges of glass transitions become narrower with the increase of Li₂O concentration.     

Methodical developments for X-ray diffraction measurements and data analysis on lyotropic liquid crystals applied to K-soap/glycerol systems

 X-ray diffraction (XRD) data acquisition and processing software measurements on long-spacing binary systems, including adapted noise reduction algorithms, has been developed. The computation of XRD patterns has been summarized and the origin of the distinct patterns of long-spacing compounds has been illustrated with the aid of such simulations. This also provided the possibility to evaluate the retrievable amount of information used for graphical or numerical indexing programs. Numerical indexing programs were applied and limits of indexing method have been discussed. Differential scanning calorimetry (DSC) measurements and temperature-dependent XRD measurements have been carried out for the concentrations x _{KC 12} = 0.50 and 0.30 of the K-laurate/glycerol system. The analysis of the small- and wide-angle diffractograms in the various phase regions of the binary system as well as the DSC measurements provided the following results: – The creation of the lamellar phase extends over a temperature range of ΔT≈ 20 K at a concentration of x _{KC 12} = 0.50. The lamellas show a reduced degree of order. – The crystalline-to-gel phase transition is accompanied by a leap in the d values corresponding to the small-angle reflexes. Also a distinct splitting of the small-angle reflexes is observed within the gel phase. Simultaneously a rearrangement and intensity decay of the wide-angle reflexes occurs. Since some wide-angle reflexes are still present, the structure can be considered to have a partially reduced three-dimensional order. – During the creation of lamellar phases the d value decreases sharply with rising temperature. This decrease of d can be interpreted as a further decay of molecular order in the hydrocarbon chains of the K-laurate within the bilayers. – The XRD measurements correlate with the DSC data. According to our measurements a revision of the phase diagram with respect to the actual extension of the gel-phase region was necessary. Received: 3 March 1999 Accepted in revised form: 29 March 1999     

Phase and aggregation behaviour of double-chain cationic surfactants from the class of N-alkyl-N-alkyl′-N, N-dimethylammonium bromide surfactants

We present the phase diagrams and the properties of newly synthesised double-chain cationic N-alkyl-N-alkyl′-N,N-dimethylammonium bromide surfactants [C _x C _y DMABr (x = 12, 14 and 16; y = 10, 11, 12, 14 and 16)]. All the systems studied form liquid-crystalline lamellar phases but with different morphologies: unilamellar vesicles at low surfactant concentrations, multilamellar vesicles and tubular aggregates for surfactant concentrations between 2 and 10 wt% and at even higher concentrations planar bilayers of surfactant molecules in the classical L_α phase. The phase diagrams were determined with macroscopic and microscopic methods (polarisation microscopy, freeze-fracture transmission electron microscopy, scanning electron microscopy and differential interference contrast microscopy). The properties of the surfactant solutions were determined with differential scanning calorimetry measurements for Krafft point determination and small-angle neutron scattering measurements for interlamellar spacing and bilayer thickness. Finally, conductivity and viscosity measurements for phase characterisation were carried out. Received: 7 April 1999 Accepted in revised form: 30 April 1999     

Sum frequency generation spectroscopic study of the condensation effect of cholesterol on a lipid monolayer

Sum frequency generation (SFG) spectra and surface pressure–molecular area (π–A) isotherms have been obtained for mixed cholesterol–DPPC monolayers with cholesterol mole fractions, x(chol.), from 0 to 1.0, at the air–water interface, under same conditions, at 22 °C. Analysis of the spectra indicated that incorporation of cholesterol into the monolayers at 3 mN m⁻¹ greatly increases the conformational and orientational order of the alkyl chains of DPPC, maximizing these properties at x(chol.)=0.4. Analysis also indicated that order in the mixed monolayers at 15 and 35 mN m⁻¹ is not affected by incorporation of cholesterol. The π–A isotherms measured at 3 mN m⁻¹ for the mixed monolayer with x(chol.)=0.4 have the largest negative deviation of the molecular area relative to those of ideal mixtures (the so-called “condensation effect” of cholesterol), indicating the most thermodynamically stable state. Comparison of results from SFG spectra and π–A isotherms explicitly proved that the condensation effect can be interpreted in terms of conformational and orientational ordering of the alkyl chains of DPPC.     

Size-controlled synthesis of CuO–ZrO<Subscript>2</Subscript> nanoparticles prepared through reverse micelle method

In this research, CuO–ZrO₂ nanoparticles are synthesized using microreactors made of surfactant/water/cyclohexane microemulsions. The effect of different microemulsion variables on the particle size and its distribution, such as water-to-surfactant molar ratio (W ₀) and different surfactants are discussed. Three different surfactant types including cationic (CTAB), anionic (AOT), and nonionic (Brij56) are used. Also a different amount of water to surfactant in nano composite synthesis is used. The powders were characterized by DTA/TG, XRD, SEM, EDS, TEM and BET techniques and their physical properties are compared. The results show a decrease of particles size in presence of cationic surfactant. Narrow particles size distribution of the resultant CuO–ZrO₂ nanocomposite in presence of cationic surfactant, anionic and nonionic surfactant is compared. Also for AOT surfactant, by raising water to surfactant molar ratio the particles size is increased and the optimum ratio is H₂O: Surfactant = 0.32:0.055, respectively.     

Calorimetric and spin-label ESR studies of PEG:2000-DPPE containing DPPC/lyso-PPC mixtures

The thermotropic behavior of dipalmitoylphosphatidylcholine (DPPC) multibilayers containing up to 10 mol% of lyso-palmitoylphosphatidylcholine (lyso-PPC) with and without low content of poly(ethylene glycol:2000)-grafted dipalmitoylphosphatidylethanolamine (PEG:2000-DPPE) has been studied by high sensitivity differential scanning calorimetry (DSC) and electron spin resonance (ESR) using the spin probe di-tert-butyl-nitroxide (DTBN). The three lipids, dispersed in buffer at appropriate concentrations, form thermosensitive liposomes used as site-specific drug-delivery systems. Without polymer–lipids, the DPPC main transition temperature is downshifted of 1.2–1.3 °C at the highest lyso-PPC content. The molar enthalpy and the cooperative unit of the DPPC main transition first decrease rapidly, then more slowly and finally slightly increase with lyso-PPC content. Moreover, in the mixed dispersions, the membrane fluidity increases at any temperature. The addition up to 5 mol% of PEG:2000-DPPE to DPPC/10 mol% lyso-PPC mixtures does not affect neither the thermotropic phase behavior nor the transition cooperativity and the fluidity of the dispersions.     

Growth of silica nanoparticles in methylmethacrylate-based water-in-oil microemulsions

The mechanism of silica particle formation in monomer microemulsions is studied using dynamic light scattering (DLS), atomic force microscopy, small-angle X-ray scattering (SAXS), and conductivity measurements. The hydrolysis of tetraethylorthosilicate (TEOS) in methylmethacrylate (MMA) microemulsions (MMA = methylmethacrylate) is compared with the formation of SiO₂ particles in heptane microemulsions. Stable microemulsions without cosurfactant were found for MMA, the nonionic surfactant Marlophen NP10, and aqueous ammonia (0.75 wt%). In the one-phase region of the ternary phase diagram, the water/surfactant ratio (R _w) could be varied from 6 to 18. The DLS and SAXS measurements show that reverse micelles form in these water-in-oil (w/o) microemulsions. The minimum water-to-surfactant molar ratio required for micelle formation was determined. Particle formation is achieved from the base-catalyzed hydrolysis of TEOS. According to atomic force microscopy measurements of particles isolated from the emulsion, the particle size can be effectively tailored in between 20 and 60 nm by varying R _w from 2–6 in heptane w/o microemulsions. For MMA-based microemulsions, the particle diameter ranges from 25 to 50 nm, but the polydispersity is higher. Tailoring of the particle size is not achieved with R _w, but adjusting the particle growth period produces particles between 10 and 70 nm.     

The interaction between sodium dodecylsulfate and the cationic-nonionic random copolymer (3-(2-methylpropionamide)propyl) trimethylammonium chloride–acrylamide of two different charge densities studied using dynamic light scattering and rheometry

The effects of complex formation between sodium dodecylsulfate (SDS) and the positively charged (3-(2-methylpropionamide)propyl)trimethyl-ammonium chloride-acrylamide (MAPTAC-AM) copolymer have been studied in dilute and semidilute aqueous solution in the presence of 10 mM NaCl. Two different charge densities of the copolymer have been used in the study: 0.31 and 0.66, corresponding to the proportion of MAPTAC units. Dynamic light scattering (DLS) and rheometry (static low-shear and capillary viscometry) have been performed on the systems at different charge ratios, i.e., SDS/MAPTAC molar ratios, r. Regarding the phase behavior, the maximum binding ratio prior to precipitation differs between the copolymers. A 1.0% w/v solution of SDS/31% MAPTAC-AM is soluble at r = 0.4 , while an SDS/66% MAPTAC-AM solution of 1.0% w/v shows phase separation at this ratio. With excess surfactant, the complex in the former system is resolubilized at r=2.0, whereas the latter system is still phase-separated at r=5.0. DLS results show that, for both copolymers, the hydrodynamic radius, R _h, of the single-chain copolymer-surfactant complex decreases as a function of r, but then increases slightly prior to phase separation. The corresponding hydrodynamic virial coefficient, k _D, changes in the same manner as R _h. The light-scattering data also show that the formation of larger structures is promoted as the polymer concentration is increased from 0.2 to 1.0% w/v. This is shown by the increase in the relative aggregate-to-single coil peak areas in the relaxation time distributions. Both systems have this common trend. The results from rheological measurements support the results from DLS. A reduction in intrinsic viscosity, [η], is observed on increasing r up to phase separation. The major part of the static low-shear measurements showed Newtonian behavior for both systems at different copolymer concentrations (27.6–138 mM), and at different r. These systems, partially ionic polymer/oppositely charged surfactant, present very interesting rheological behavior at relatively high polymer concentrations and at low r values. Their behavior is similar to those of hydrophobically modified polyelectrolytes. Received: 17 June 1998 Accepted: 12 August 1998     

The structure and electrochemical characteristics of La0.67Mg0.33 (Ni0.8Co0.1Mn0.1) x (x=2.5–5.0) multiphase alloys for nickel-metal hydride batteries

This paper presents results concerning structure and electrochemical characteristics of the La_0.67Mg_0.33 (Ni_0.8Co_0.1Mn_0.1) _x (x=2.5–5.0) alloy. It can be found from the result of the Rietveld analyses that the structures of the alloys change obviously with increasing x from 2.5 to 5.0. The main phase of the alloys with x=2.5–3.5 is LaMg₂Ni₉ phase with a PuNi₃-type rhombohedral structure, but the main phase of the alloys with x=4.0–5.0 is LaNi₅phase with a CaCu₅-type hexagonal structure. Furthermore, the phase ratio, lattice parameter and cell volume of the LaMg₂Ni₉phase and the LaNi₅ phase change with increasing x. The electrochemical studies show that the maximum discharge capacity increases from 214.7 mAh/g (x=2.5) to 391.1 mAh/g (x=3.5) and then decreases to 238.5 mAh/g (x=5.0). As the discharge current density is 1,200 mA/g, the high rate dischargeability (HRD) increases from 51.1% (x=2.5) to 83.7% (x=3.5) and then decreases to 71.6% (x=5.0). Moreover, the exchange current density (I ₀) of the alloy electrodes first increases and then decrease with increasing x from 2.5 to 5.0, which is consistent with the variation of the HRD. The cell volume reduces with increasing x in the alloys, which is detrimental to hydrogen diffusion and accordingly decreases the low-temperature dischargeability of the alloy electrodes.     

New doped Li-M-Mn-O (M = Al, Fe, Ni) spinels as cathodes for rechargeable 3 V lithium batteries

The electrochemical behaviour of new doped Li-M-Mn-O (M = Al, Fe, Ni) spinel oxides in liquid electrolyte lithium cells was studied. The insertion electrode materials were obtained by heating stoichiometric amounts of thoroughly mixed LiOH and M _x Mn_{1− x} CO₃ (M = Fe, Ni; x = 0.08−0.15) or Al _x Mn_{1− x} (CO₃) (OH) _y , in the case of Al, at 380 °C in air for 20 h. The transition metal-doped samples, particularly those containing Ni or obtained at low temperatures, where the resulting spinel was cation-deficient and highly disordered, exhibited the best cycling performance in the potential window 3.3−2.3 V. Cell capacity was retained by 80% after 200 cycles. Capacity fading was observed on increasing the firing temperature, together with improved crystallinity and the disappearance of cation vacancies. This impaired electrochemical behaviour is ascribed to a Jahn-Teller effect, which induces an X-ray-detectable cubic-tetragonal phase transition upon lithium insertion. The phase transition was undetectable in the low-temperature samples. The influence of the Jahn-Teller distortion is thus seemingly lessened by a highly disordered structure. Received: 25 November 1997 / Accepted: 28 January 1998     

Synchrotron SAX and WAX diffraction study of a hydrated very long-chain, dendritic amphiphile + DPPC mixture

The tri-headed anionic dendritic amphiphile, 4-(2-carboxyethyl)-4-[(icosyloxycarbonyl)amino]heptanedioic acid (3CCb20), forms mixed aggregates with dipalmitoylphosphatidylcholine (DPPC) in excess water at 3CCb20:DPPC = 0.91:1 molar ratio. On heating, these mixed aggregates transform into fluid bilayers stacked in the liquid crystalline lamellar L phase at about 40 °C. This phase transition and the microstructure of 3CCb20 + DPPC aggregates were studied with small- and wide-angle synchrotron X-ray diffraction. The ability of 3CCb20 to solubilize solidlike lipid bilayers could contribute to the antimicrobial activities of 3CCb20, including its anti-HIV activity.     

Effect of curcumin on liposome: curcumin as a molecular probe for monitoring interaction of ionic liquids with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine liposome

Recent increase and wider use of ionic liquids (ILs) for various applications has drawn attention to their toxicological consequence on human health. The present study explores effects of three different kinds of widely used ILs, such as 1‐methyl‐3‐octylimidazolium chloride, 1‐buytl‐3‐methyl imadazolium tetrafluoroborate and 1‐benzyl‐3‐methyl imidazolium tetrafluoroborate, on liposome properties of 1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphocholine (DPPC) by applying curcumin as molecular probe. Fluorescence intensity of curcumin is reported as a novel rotor which is sensitive to viscosity and thus the fluidity of the solvent. It follows a linear relationship of log fluorescence vs viscosity as proposed by Förster–Hoffmann equation. Curcumin binds strongly to liposome. At low concentration, the lipophilic drug curcumin does not appreciably influence the phase transition temperature of DPPC but as concentration reaches high levels significantly depresses the phase transition temperature. ILs diminish membrane fluidity. 1‐methyl‐3‐octylimidazolium chloride disorders membrane properties by lowering the phase transition as is observed for higher concentration of curcumin, but 1‐buytl‐3‐methyl imidazolium tetrafluoroborate and 1‐benzyl‐3‐methyl imidazolium tetrafluoroborate do not modify phase transition temperature perceptibly; rather they broaden the phase transition at low molar concentration ratio. The three different kinds of ILs under study behave similarly at a high IL:DPPC ratio (1:2), while they behave differently at lower ratios (1:10–1:5).     

Phase diagram and electrical conductivity of the DyBr<Subscript>3</Subscript>–RbBr binary system

Phase equilibrium in the DyBr₃–RbBr binary system was established from differential scanning calorimetry measurements. This system exhibits three compounds, namely Rb₃DyBr₆, Rb₂DyBr₅, and RbDy₂Br₇, and two eutectics located at DyBr₃ molar fraction x = 0.116 (T = 886 K) and x = 0.458 (T = 702 K), respectively. Rb₃DyBr₆ undergoes a solid–solid phase transition at 726 K and melts congruently at 1,059 K. Rb₂DyBr₅ and RbDy₂Br₇ melt incongruently at 737 and 748 K, respectively. The electrical conductivity of DyBr₃–RbBr liquid mixtures was measured over the whole composition range. Results obtained are discussed in term of possible complex formation.     

Excess enthalpies of water+1,4-dioxane at 278.15, 298.15, 318.15 and 338.15 K

The excess molar enthalpies of (1–x)water+x1,4-dioxane have been measured at four different temperatures. All the mixtures showed negative enthalpies in the range of low mole fraction but positive ones in the range of high mole fraction of 1,4-dioxane. Excess enthalpies were increased with increasing temperature except those of at 278.15 K. Partial molar enthalpies have maximum around x=0.13 and minimum around x=0.75. Three different behaviors for the concentration dependence of partial molar enthalpies were observed for all temperature. Theoretical calculations of molecular interactions of three characteristic concentrations were carried out using the molecular orbital method.     

Rubidium and lithium butanoates binary phase diagram

The temperature and enthalpy vs. composition diagrams of the binary system [xC₃H₇CO₂Li+(1–x)C₃H₇CO₂Rb], where x=mole fraction, were determined by differential scanning calorimetry (DSC). This binary systems displays the formation of two mixed salts with a composition 1:1 and 1:2, which melt incongruently at T _fus=590.5 K, with Δ_fus H _m=11.6 kJ mol^–1, and congruently at T _fus=614.5 K, with Δ_fus H _m=20.2 kJ mol^–1, respectively. The phase diagram also presents an ionic liquid-crystalline phase in a wide temperature range: 95 K.     

Segregation and phase transition in mixed lipid films

Energy dispersion X-ray diffraction (EDXD) was applied to investigate the structure of partly dehydrated mixed films formed by the phospholipid dimyristoyl phosphatidylcoline (DMPC) and any of the three diastereomers of the dicationic gemini surfactant (2S,3S)-2,3-dimethoxy-1,4-bis(N-hexadecyl-N,N-dimethylammonium) butane dibromide. As the surfactant to lipid molar ratio (R(S/L)) increases, the gemini monotonically solubilizes the lipid bilayer promoting the formation of a cubic phase of space group Pmn segregating from the residual lamellar phase of the lipid. Finally, at R(S/)(L) = 1, the phase transition is complete. The mixed film at the highest surfactant to lipid molar ratio (R(S/L) = 2.3) was hydrated by a vapor saturated atmosphere. At full hydration, a cubic to lamellar phase transition occurs. Coarse grain dynamic investigations, carried out as a function of both the surfactant to lipid molar ratio and the number of water molecules for amphiphile unit, allowed us to elucidate the structure of the emerging cubic phase and the hydration-induced structural pathway of the cubic to lamellar phase transition observed by EDXD.     

Catalytic soot combustion of α-Fe/Ce–K–O nanocomposites via citrate-gel route

The binary phase, porous, nanocomposite xα-Fe/(1 − x)Ce_0.9–K_0.1–O (x = 0.05–0.2) catalysts and the catalyst-coated honeycomb ceramic device have been prepared by the citrate-gel thermal decomposition-reduction process and the sol–gel assisted dip-coating method, respectively. The nanocomposite of fluorite-type structure CeO₂ nanoparticles about 18–51 nm and α-Fe nanoparticles about 32 nm is obtained at 600 °C for 2 h in a deoxidization atmosphere and the α-Fe in nanocomposite has the suppression effect on grain growth of CeO₂. With Fe content increasing from 0.05 to 0.1, the specific surface area for the nanocomposites increases dramatically from about 4.4 to 43.0 m²/g, reaching a maximum value 57.7 m²/g at x = 0.15, and the pores vary from macropores to micro- or mesopores. Due to the presence of nano α-Fe, all the catalysts exhibit a very high soot catalytic activity, with the lowest T₂₀ (255 °C) and T₅₀ (291 °C) for the nanocomposite with x = 0.15, and it is confirmed by the bench test under practical diesel exhaust gases.