Hydrogels from phospholipid vesicles

It is shown that phospholipid dispersions with a few percent of diacylphosphocholine PC in water can be swollen to single-phase lyotropic liquid crystalline L_α-phases by the addition of co-solvents like glycerol, 1,3-butyleneglycol BG or 1,2-propyleneglycol PG. The birefringent L_α-phases contain small unilamellar and multilamellar vesicles if the temperature of the samples is above the Krafft-Temperature T_m of the phospholipid. When such transparent birefringent viscous samples are cooled down below T_m the samples are transformed into birefringent gels. Cryo-TEM and FF-TEM measurements show that the bilayers of the vesicles are transformed from the liquid to the crystalline state during the transformation while the vesicle structure remains. The bilayers of the crystalline vesicles form adhesive contacts in the gel. Pulsed-field gradient NMR measurements show that two different kinds of water or co-solvent can be distinguished in the gels. One type of solvent molecules can diffuse like normal solvent in a continuous bulk phase. A second type of water diffuses much more slowly. This type of solvent is obviously trapped in the vesicles. The permeability of the crystalline vesicles for water and solvent molecules is much lower in the crystalline state than in the fluid state.     

Phase behavior and rheological properties of lecithin/TTAOH/H<Subscript>2</Subscript>O mixtures

The phase behavior, structures, and rheological properties of lecithin/tetradecyltrimethylammonium hydroxide (TTAOH)/water system were investigated by cryogenic transmission electron microscopy (cryo-TEM), polarization optical microscope, ¹H and ³¹P nuclear magnetic resonance (NMR) spectra, surface tension, and rheological measurements. With the variation of mixing molar ratios and concentrations of lecithin and TTAOH, the system exhibits the phase transition from micelles (L₁ phase) to vesicles (L_α phase) through a phase separation region. The rod-like micelles, uni- and multilamellar vesicles were determined by means of cryo-TEM observations. The surface tension and rheological measurements were performed to follow the phase transition. The samples of L₁ phase region behave as Newton fluids at low concentration of lecithin. With the increase of the lecithin concentration, a shear-thinning L₁ phase at the shearing rate 100 s⁻¹ was found. The samples of \textL_a {{\text{L}}_{\alpha }} phase region show viscoelastic properties of the typical vesicles. The interactions between lecithin and TTAOH were monitored by ¹H and ³¹P NMR spectra. These results could contribute towards the understanding of the basic function of lecithin in biological membranes and membranous organelles.     

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.     

Thermal behavior of trehalose dihydrate (T h) and β-anhydrous trehalose (T β) by in-situ laboratory parallel-beam X-ray powder diffraction

Thermal behaviors of trehalose dihydrate (T _h) and β-anhydrous trehalose (T _β) have been investigated by in-situ laboratory parallel-beam X-ray powder diffraction. Data indicate that both phases show essentially the same volume expansion but expansion of the anhydrous form is markedly anisotropic due to the features of the hydrogen-bond network. Under the present experimental conditions, dehydration starts at 66 °C and within the 75 < T < 114 °C the presence of the T _α anhydrous polymorphic form has been detected.     

DODAB and DODAC bilayer-like aggregates in the micromolar surfactant concentration domain

In the millimolar concentration domain (typically 1 mM), dioctadecyldimethylammonium bromide and chloride (DODAX, X representing Br⁻ or Cl⁻ counterions) molecules assemble in water as large unilamellar vesicles. Differential-scanning calorimetry (DSC) is a suitable technique to obtain the melting temperature (T _m) characteristic of surfactant bilayers, while fluorescence spectroscopy detects formation of surfactant aggregates, like bilayers. These two techniques were combined to investigate the assembly of DODAX molecules at micromolar concentrations, from 10 to 100 μM. At 1 mM surfactant, T _m ≈ 45 °C and 49 °C, respectively, for DODAB and DODAC. DSC and fluorescence of Nile Red were used to show the formation of DODAX aggregates, at the surfactant concentration as low as 10 μM, whose T _m decreases monotonically with increasing DODAX concentration to attain the value for the ordinary vesicles. The data indicate that these aggregates are organized as bilayer-like structures.     

Hydrate formation in the tetraethylammonium hydroxide-water system

A phase diagram of the tetraethylammonium hydroxide-water binary system was studied by differential thermal analysis. Seven crystal phases of tetraethylammonium hydroxide were found. Two of them are stable: tetrahydrate (T _m = 47.0°C), two phases of a compound with the hydration number 7.5 (T _m = −18.1 and −23.2°C); five are metastable phases: two polymorphs of pentahydrate (T _m = 39.4 and 0.9°C), hexahydrate (T _m = −70.1°C), and a compound with hydrate number 10–11 (T _m = −112°C).     

Influence of the chain length of K-soaps on the phase diagram and structural parameters of nonaqueous liquid crystals and the gel phase in K-soap/glycerol binary systems

 Analogously to the aqueous K-soap/water systems already examined, the five glycerol · (Gl)-containing systems KC _n /Gl (n = 12, 14, 16, 18, 22) also built up hexagonal (H_α), lamellar (L_α), isotropic micellar (S), gel-like (G) and crystalline phases (C). These phases were identified by texture observations with a polarizing microscope, by differential scanning calorimetry measurements and by X-ray diffraction investigations. The appertaining phase regions were plotted in the binary phase diagram. Binary Gl-containing K-soap systems have the following properties. The H_α phase is built up at low soap concentration. The L_α phase is formed at high soap concentrations. The temperature of the phase transition H_α ⇆ S runs through a maximum. Increasing the chain lengths of the soaps shifts the formation of the H_α phase to lower soap concentration. A strong correlation between the chain length of K-soaps and the d values of L_α, H_α, G and C phases is found. Based on the comparison of the X-ray diffractograms of the G phase a structural model is proposed. The G phase consists of two groups of domains with two different dimensions. Received: 9 August 1999/Accepted in revised form: 20 September 1999     

Influence of <Emphasis Type="Italic">m</Emphasis>-isopropenyl-α,α-dimethylbenzyl isocyanate and styrene on non-isothermal crystallization behavior of polypropylene

Non-isothermal crystallization kinetics of polypropylene (PP), m-isopropenyl-α,α-dimethyl-benzyl isocyanate grafted PP (PP-g-m-TMI), and styrene(St), as comonomer, together with m-TMI grafted PP (PP-g-(St-m-TMI)) was investigated by using differential scanning calorimetry (DSC) under different cooling rates. The crystallization rates of all samples increased with increasing cooling rate. The relation of the half time of crystallization (t _1/2) of the three samples, t _{1/2(PP-g-(St-m-TMI))} < t _{1/2(PP-g-m-TMI)} < t _1/2(PP), implying the introduction of St could effectively improve the degree of grafting of m-TMI, resulting in crystallization temperature increased, and the crystallization rate was the fastest. Three methods, namely, the Avrami, the Ozawa, and the Mo, were used to describe the crystallization process of the three samples under non-isothermal conditions. The Avrami and Ozawa neglected the secondary crystallization that follows primary crystallization. The Mo method can successfully describe the overall non-isothermal crystallization process of all the samples. It has been found that the F(T)_{(PP-g-(St-m-TMI))} < F(T)_(PP-g-m-TMI) < F(T)_(PP), also meaning that the crystallization rate of PP-g-(St-m-TMI) and PP-g-m-TMI were faster than that of PP. The activation energy (ΔE) for non-isothermal crystallization of all samples was determined by using the Kissinger method. The result showed that the lower value of ΔE for crystallization obtained for PP-g-m -TMI and PP-g-(St-m-TMI) confirmed the nucleating effect of St and m-TMI on crystallization of PP.     

Succinic or glutaric anhydride modified linear unsaturated (epoxy) polyesters

A series of N-alkyl-N-alkyl′-pyrrolidinium-bis(trifluoromethanesulfonyl) imide (TFSI⁻) room temperature ionic liquids (RTILs) has been investigated by means of thermogravimetric analysis (TG), differential scanning calorimetry, FT-IR spectroscopy, and X-ray diffraction analysis. These compounds exhibit a thermal stability up to 548–573 K. The mass loss starting temperature, T _ml, falls in a narrow range of temperatures: 578–594 K. FT-IR spectra, performed before and after 24 h isothermal experiments at 553 and 573 K, have confirmed their great thermal stability. Below the ambient temperature, these compounds exhibit a complex behavior. N-methyl-N-propyl-pyrrolidinium-TFSI is the sole liquid which crystallizes without forming any amorphous phase even after quenching in liquid nitrogen. Its crystalline phase has a melting point, T _m, of 283 ± 1 K. When the amorphous solid is heated, the N-butyl-N-ethyl-pyrrolidinium-TFSI presents a glass transition temperature, T _g, at 186 K followed by a cold crystallization, T _cc, at 225 K, and a final T _m at 262 K. The N-butyl-N-methyl-pyrrolidinium-TFSI exhibits a T _g between 186 and 181 K, its cold crystallization leading to two different solid phases. Solid phase I has a melting point T _I,m = 252 K and phase II, T _II,m = 262 K. When the amorphous phase is obtained at a cooling rate of 10 K/min, its T _cc is 204 K, and a metastable solid phase (III) is obtained which transforms into the phase II at 226 K. However, when the sample is quenched, the amorphous phase transforms into phase II at T _cc = 217 K and phase I at 239 K. P₁₅-TFSI exhibits the most complicated pattern as, on cooling, it leads to both a crystallized phase at 237 K and an amorphous phase at 191 K. On heating, after a T _g at 186 K and a T _cc at 217 K, two solid–solid phase transitions are observed at 239 K and 270 K, the final T _m being 279 K.     

Structural and calorimetric investigations on nonaqueous liquid crystals and gel phases in the binary system K-stearate/glycerol

The K-stearate/glycerol (KC₁₈/Gl) binary system was studied at mole fractions of stearate of x _KC18 = 0.10, 0.25, 0.30 and 0.50. Small- and wide-angle X-ray diffraction (XRD) measurements were combined with differential scanning calorimetry (DSC) measurements at different temperatures. The investigations were intended to verify the previously published phase diagram and were targeted at the confirmation of the gel-like (G₁) phase and the isotropic (I) phase. The XRD and DSC measurements lead to the conclusion that the G₁ phase as well as the I phase, the existence of which had been proposed from texture observations, do in fact not exist. Consequently, a correction of the preliminary phase diagram is given. This corrected phase diagram reveals the crystalline phase (C) ⇆ gel phase (G) ⇆ hexagonal phase (H_α) ⇆ isotropic, micellar phase phase transitions for low KC₁₈ concentrations of x _KC18 = 0.15–0.3 and the C ⇆ G ⇆ lamellar phase (L_α) phase transitions for concentrations about or higher than x _KC18 = 0.35. The C, G, L_α and H_α phases have been further characterized by structural parameters (characteristic d values) as a function of temperature. The phase transitions C ⇆ G, G ⇆ L_α and G ⇆ H_α correlate with sharp shifts in the d value of the first small-angle reflections. Received: 20 April 1999 Accepted: 28 July 1999     

Phase behavior and solution properties of sodium (3-dodecanoyloxy-2-hydroxy-propyl) succinate in water

Sodium (3-dodecanoyloxy-2-hydroxy-propyl) succinate (SLGMS) is a conjugated anionic surfactant in which a glycerol residue connects with a hydrophilic sodium succinate and dodecanoate. Aqueous micellar phase (W_m), hexagonal (H₁), bicontinuous cubic (V₁), and lamellar (L_α) phases are successively formed with increasing the surfactant concentration in a binary SLGMS-water system. The Krafft point is below 0 °C. The effective cross sectional area per surfactant molecule, a _s, in the H₁ phase is almost constant, 0.5 nm², and the shape of cylindrical micelle is almost unchanged with surfactant concentration. The cmc value of SLGMS measured by means of surface tension, electrical conductivity, and fluorescence probe methods is in the range of 4∼9 × 10⁻⁵ mol/l that is much lower than that of sodium dodecanoate, 2 × 10⁻² mol/l, or SDS, 8 × 10⁻³ mol/l. Hence, it is considered that the polar glycerol part in the SLGMS acts as a hydrophobic part. The solubilization of oil in the SLGMS solution is much higher than that in the SDS solution and this also suggests that the glycerol and succinic units act as lipophilic moieties. Received: 15 June 2000/Accepted: 27 July 2000     

Thermodynamic investigation of effect of salt concentrations on denatured α-Amylase adsorbed onto a moderately hydrophobic surface

The displacement adsorption enthalpies (ΔH) of denatured α-Amylase (by 1.8 mol L⁻¹ GuHCl) adsorbed onto a moderately hydrophobic surface (PEG-600, the end-group of polyethylene glycol) from solutions (x mol L⁻¹ (NH₄)₂SO₄, 0.05 mol L⁻¹ KH₂PO₄, pH 7.0) at 298 K are determined by microcalorimeter. Further, entropies (ΔS), Gibbs free energies (ΔG) and the fractions of ΔH, ΔS, and ΔG for net adsorption of protein and net desorption of water are calculated in combination with adsorption isotherms of α-Amylase based on the stoichiometric displacement theory for adsorption (SDT-A) and its thermodynamics. It is found that the displacement adsorptions of denatured α-Amylase onto PEG-600 surface are exothermic and enthalpy driven processes, and the processes of protein adsorption are accompanied with the hydration by which hydrogen bond form between the adsorbed protein molecules favor formation of β-sheet and β-turn structures. The Fourier transformation infrared spectroscopy (FTIR) analysis shows that the contents of ordered secondary structures of adsorbed α-Amylase increase with surface coverages and salt concentrations increment.     

Stabilization of gas chromatographic stationary phases with nanosized particles

Summary Stabilization of polar and apolar stationary phases with nanosized particles has been demonstrated for gas chromatographic capillary columns. Mixtures of small amounts of (2–10%) of solid particles and liquids form gels, which preserve the stability of the films of stationary phases on the column walls. The stabilization effect of polar and apolar particles has been studied by determining some rheological properties of gels (flow curves, temperature dependence of yield stress values) and validated by gas chromatographic measurements using the most polar and apolar stationary phases. Dedicated to the memory of late Dr. Gábor Alexander, who was the inventor of this film stabilization method, and took active part in the early experiments.     

Influence of the specific surface area on crystallization process kinetics of some silica gels

The influence of the specific surface area on the crystallization processes of two silica gels with different specific surface areas has been investigated in non-isothermal conditions using DTA technique. The activation energies of the crystallization processes were calculated using four isoconversional methods: Ozawa-Flynn-Wall, Kissinger-Akahira-Sunose, Starink and Tang. It has been established that, the decrease of the surface area from S=252.62 m² g⁻¹, in the case of sample GS2, to S=2.52 m² g⁻¹, in the case of sample GS1, has determined a slight increase of the activation energy of the crystallization process of the gels. Regardless of the isoconversional method used, the activation energy (E _α) decreases monotonously with the crystallized fraction (α), which confirms the complex mechanism of gels crystallization. It has been proved that the Johnson-Mehl-Avrami model cannot be applied for the crystallization processes of the studied silica gels.     

Structural and calorimetric investigations on nonaqueous liquid crystals and gel phases in the binary system K-behenate/glycerol

Two mixtures of the binary system K-behenate/glycerol, x _KC22 = 0.30 and 0.50 (x = mole fraction), have been investigated as a function of temperature using small- and wide-angle X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The binary phase diagram based on texture observations using polarizing optical microscopy was confirmed. XRD and DSC measurements provided concordant results with respect to the range of the phase regions in the phase diagram. Only differences between the DSC curves for rising and falling temperatures were detected. The recorded XRD and DSC data of the liquid crystals and gel phases observed are also in agreement with previously reported investigations on K-soap/glycerol. The C ⇆ G and G ⇆ L_α phase transitions correlate with a sharp shift in the d value of the first small-angle reflection. The G phase is characterized by a split of the first small-angle reflections. Also, the position and shape of the wide-angle reflections change and the peak intensity is reduced. Received: 5 July 1999 Accepted in revised form: 27 July 1999     

Influence of cobalt complex on thermal properties of poly(ethylene terephthalate)/polycarbonate blend

The effects of processing time and concentration of cobalt acetylacetonate III complex in poly(ethylene terephthalate)/polycarbonate reactive blending were investigated. The blend was prepared in an internal mixer at 270°C, 60 rpm, at different processing times (5–20 min) and catalyst concentration (0.00625–0.075 mass%). The reaction product was evaluated by differential scanning calorimetry (DSC), thermogravimetry (TG) and wide angle X-rays scattering (WAXS). In general, the DSC curves showed two glass transition temperatures (T _g’s) close to each homopolymer, independent of the processing time and complex’s concentration, suggesting the presence of two phases: one rich in PET and other one rich in PC. In all cases, melting temperature (T _m), cold crystallization temperature (T _cc) and crystallinity degree (X _c) were progressively reduced with blending conditions. The TG curves presented two decays. The first one represented the PET rich phase and the other one was related to the PC phase. The WAXS diffractograms showed that the Bragg’s angle and interplanar spacing of PET remaining practically unchanged.     

Volumetric Properties of Aqueous Solutions of L-Glutamic Acid and Magnesium-L-Glutamate

Densities of aqueous solutions of L-glutamic acid and magnesium-L-glutamate were determined from T=288.15 to 333.15 K at 5 K temperature intervals. The measured densities were used to evaluate the apparent molar volumes, V _2,φ (m,T), the cubic expansion coefficients, α(m,T), and the changes of isobaric heat capacities with respect to pressure, (∂ C _p /∂ p) _T,m . They were qualitatively correlated with changes in the structure of water that occur when L-glutamic acid or magnesium-L-glutamate are present.     

Electron microscopic and light scattering observation on a system with two iridescent phases

Electron microscopic observations and classical light-scattering measurements have been carried out for dodecyldimethylaminoxide/hexanol/water mixtures in the concentration range where iridescent colors occur. This system has two different iridescent phases. The iridescent phase with more hexanol forms quickly, and the phase with less hexanol forms very slowly. Three different isotropic phases which show strong flow birefringence are found near both iridescent phases. The electron microscopic pictures show clearly that only one of these isotropic phases with strong flow birefringence is a bicontinuous sponge phase (L_3h -phase). This is the phase which comes out by adding some alkanol to the upper lamellar phase. The flow birefringent phase below the lower lamellar phase forms unilamellar vesicles. The flow birefringent phase which occurs between both iridescent phases contains multilamellar vesicles and is shown to be a precursor of a lamellar phase.     

Sequential spectrofluorimetric determination of free and total glycerol in biodiesel in a multicommuted flow system

A new procedure for spectrofluorimetric determination of free and total glycerol in biodiesel samples is presented. It is based on the oxidation of glycerol by periodate, forming formaldehyde, which reacts with acetylacetone, producing the luminescent 3,5-diacetyl-1,4-dihydrolutidine. A flow system with solenoid micro-pumps is proposed for solution handling. Free glycerol was extracted off-line from biodiesel samples with water, and total glycerol was converted to free glycerol by saponification with sodium ethylate under sonication. For free glycerol, a linear response was observed from 5 to 70 mg L⁻¹ with a detection limit of 0.5 mg L⁻¹, which corresponds to 2 mg kg⁻¹ in biodiesel. The coefficient of variation was 0.9% (20 mg L⁻¹, n = 10). For total glycerol, samples were diluted on-line, and the linear response range was 25 to 300 mg L⁻¹. The detection limit was 1.4 mg L⁻¹ (2.8 mg kg⁻¹ in biodiesel) with a coefficient of variation of 1.4% (200 mg L⁻¹, n = 10). The sampling rate was ca. 35 samples h⁻¹ and the procedure was applied to determination of free and total glycerol in biodiesel samples from soybean, cottonseed, and castor beans.