Solubilization of carotenoids from carrot juice and spinach in lipid phases: II. Modeling the duodenal environment

We have been investigating the factors determining the bioavailability of carotenoids from vegetables. The previous paper [Rich, G.T., Bailey, A.L., Faulks, R.M., Parker, M.L., Wickham, M.S.J., and Fillery-Travis, A. (2003) Solubilization of Carotenoids from Carrot Juice and Spinach in Lipid Phases: I. Modeling the Gastric Lumen, Lipids 38, 933–945] modeled the gastric lumen and studied the solubilization pathway of carotenes and lutein from carrot juice and homogenized spinach to oil. Using the same vegetable preparations, we have extended our investigations to solubilization pathways potentially available in the duodenum and looked at the ease of solubilization of carotenes and lutein within simplified lipid micellar and oil phases present within the duodenum during digestion. Micellar solubility of raw spinach carotenoids was low and was enhanced by freezing, which involved a blanching step. The efficiency of solubilization of carotenoids in glycodeoxycholate micelles decreased in the order lutein_carrot>lutein_{blanched-frozen spinach}>carotene_{blanched-frozen spinach}>carotene_carrot. Frozen spinach carotenoids were less soluble in simple micelles of taurocholate than of glycodeoxycholate. The results comparing the solubility of the carotenoids in mixed micelles (bile salt with lecithin) with simple bile salt micelles are explained by the relative stability of the carotenoid in the organelle compared to that in the micelle. The latter is largely determined by the polarity of the micelle. Below their critical micelle concentration (CMC), bile salts inhibit transfer of carotenoids from tissue to a lipid oil phase. Above their CMC, the bile salts that solubilize a carotenoid can provide an additional route to the oil from the tissue for that carotenoid by virtue of the equilibrium between micellar phases and the interfacial pathway. Mixed micellar phases inhibit transfer of both carotenoids from the tissue to the oil phase, thereby minimizing this futile pathway.     

The Effect of NaCl on the Krafft Temperature and Related Behavior of Cetyltrimethylammonium Bromide in Aqueous Solution

This paper presents the effect of NaCl on the Krafft temperature (T _K), surface adsorption and bulk micellization of cetyltrimethylammonium bromide (CTAB) in aqueous solution. The critical micelle concentration (CMC) of CTAB in the presence of NaCl increased and then decreased with increasing temperature. Thus, the CMC–temperature data can be represented by a bell-shaped curve. The micellar dissociation (fraction of counterion binding) and energetic parameters (free energy, enthalpy and entropy changes) of both adsorption and micellization were calculated. The processes were found to be both enthalpy and entropy controlled and appeared to be more and more enthalpy driven with increasing temperature. An enthalpy–entropy compensation rule was observed for both adsorption and micelle formation. The T _K of the surfactant decreased significantly in the presence of NaCl, which is a sharp contrast to the usual behavior of the effect of electrolytes on the T _K of classical ionic surfactants. The surface excess concentrations decreased with increasing temperature. However, the values were much higher in the presence of NaCl compared to the corresponding values in pure water. The solubilization behavior of a water-insoluble dye, Sudan red B (SRB), in the micellar system was studied by the UV–visible spectrophotometric technique. The molar solubilization ratio in the presence of NaCl was found to be about three times higher than that in pure water, indicating that the solubilization of SRB in the CTAB micelles significantly increases in the presence of NaCl.     

Surface-Active Properties of Solvent-Extracted <Emphasis Type="Italic">Panax ginseng</Emphasis> Saponin-Based Surfactants

In this study, saponins were extracted from Panax ginseng root powder. The crude solvent‐extracted saponins containing triterpenoid glycosides and terpenes that were identified by TLC techniques. The critical micelle concentrations (CMC) of the saponins were determined by measuring the change in (a) the UV‐visible spectrum of iodine due to the micelle‐iodine complexation, (b) the absorption intensity of aqueous alpha‐lipoic acid due to the micellar solubilization of the drug, and (c) the surface tension due to the abrupt change in the air/liquid interface saturation by surfactants monomers. The development of new absorption peak due to the micelle‐iodine complexation, enhancement in the absorbance due to the micelle‐solubilized lipoic acid, and displacement of monomer‐micelle equilibrium to micelle formation in higher monomer concentration region are some of the physicochemical properties in which CMC could be determined. We found a CMC of 0.009% w/v.     

Mixed Micellization and Mixed Monolayer Formation of Sodium Cholate and Sodium Deoxycholate in Presence of Hydrophobic Salts Under Physiological Conditions

Mixed micellization and mixed monolayer formation of two bile salts namely sodium cholate (NaC) and sodium deoxycholate (NaDC), in the presence of sodium chloride (NaCl) and three hydrophobic salts including sodium acetate (NaAc), sodium butanoate (NaBu) and sodium hexanoate (NaHx) in 10 mM phosphate buffer (pH 6.5) at 37 °C were investigated by means of surface tension measurements. The experimental results were utilized to evaluate various parameters like critical micellar concentration (CMC), micellar and monolayer interaction parameter (β and β ^σ), micellar and monolayer mole fractions (X and Z), activity coefficients of two bile salts in mixed micelles and monolayer (f and f _(σ)), surface excess (Γ_max) and minimum surface area per molecule of bile salt (A _min). Mixed micelles and mixed monolayer were found to show slight non-ideality and both these phenomena have been found to be affected differently in the presence of various additive salts with NaHx showing larger effects. Higher efficiency of NaHx in affecting both phenomena has been attributed to its appreciable hydrophobicity and surface activity, thus showing stronger interactions with bile salt molecules.     

Interaction of Azo Dye with Cationic Surfactant Under Different pH Conditions

The aggregation induced by Alizarin Yellow R (AYR) in the cationic surfactant, cetyltrimethylammonium bromide (CTAB), was investigated by measuring their UV–visible absorption spectra. Conductance measurements as a function of surfactant concentration below and above the critical micelle concentration (CMC) were studied. CTAB aggregation takes place at the concentration far below its normal CMC in the presence of AYR. Both hydrophobic and electrostatic interactions affect the aggregation process in aqueous solution. The dye effect on the CMC of CTAB was noted by a specific conductivity method as well. AYR–CTAB binding constant (K_s) and water–micelle partition co-efficient (K_x) were quantified with the help of mathematical models employed to determine the partitioning of organic additives in the micellar phase. The number of dye molecules per micelle was estimated at particular CTAB concentrations above CMC, during this study.     

Ethoxy Carboxylate Extended Surfactant: Micellar,Adsorption and Adsolubilization Properties

The micellar, adsorption, and adsolubilization properties of a novel ethoxy carboxylate extended surfactant are measured and compared to an extended sulfate surfactant. The critical micelle concentration (CMC) of the ethoxy carboxylate extended surfactant is measured to be 0.02 mM while it is 0.07 mM for the extended sulfate surfactant. Adsorption and adsolubilization studies are carried out on alumina oxide surfaces. The extended sulfate surfactant has a higher maximum adsorption capacity onto the aluminum than the ethoxy carboxylate extended surfactant (0.47 vs. 0.14 mmol/g, respectively). For adsolubilization, the extended sulfate surfactant shows a slightly higher phenanthrene adsolubilization compared to the ethoxy carboxylate extended surfactant (log K_adm of 6.15 vs. 5.71, respectively). In contrast, for solubilization, the ethoxy carboxylate extended surfactant exhibits higher phenanthrene solubilization capacities than the extended sulfate surfactant (log K_mic of 5.61 vs. 5.42, respectively). Relative to surfactant loss from the solid surface, the ethoxy carboxylate extended surfactant shows a higher desorption capacity as compared to the extended sulfate surfactant. From these measurements, the ethoxy carboxylate extended surfactant has better properties for micellar applications (lower CMC, higher K_mic), while the extended sulfate surfactant has better properties for admicellar applications (higher q_max and K_adm values, and less desorption).     

Effects of pH and Surfactant Precipitation on Surface Tension and CMC Determination of Aqueous Sodium n-Alkyl Carboxylate Solutions

Aqueous solutions of sodium tetradecanoate (S14C) and sodium dodecanoate (S12C) were used to evaluate complicated precipitation phenomena and to monitor the effects of bulk pH adjustments on surface tension and critical micelle concentrations (CMC) determination from surface tension plots. Limited solubilities of pure sodium n-alkyl carboxylates in solution near the CMC have been reported previously many times. In this study, precipitation encountered with solutions prepared from vender-supplied S12C was eliminated through additional purification. As sodium alkyl carboxylates discussed in the literature are commonly used as received from the manufacture without additional purification, the wide range of reported CMC values as well as precipitation near the CMC for S12C are also likely due to impurities. However, complete solubility for S14C solution concentrations near the reported CMC values was not obtained through additional purification of purchased material. Hence, some CMC values reported in the literature for S14C should be reconsidered, as discontinuities in the slope of surface tension versus concentration plots are likely caused by the formation of a precipitate not micelle aggregation. In addition and in agreement with other studies, solution pH adjustments revealed a minimum surface tension for maximum solubility near the pK _a value for S14C.     

Properties of aqueous solutions for two binary mixed systems between two kinds of bile salts and nonionic surfactants

The micellar properties of aqueous binary mixed solutions for two systems consisting of sodium cholate (NaC)-octaoxyethylene glycol mono n-decyl ether (C₁₀E₈) and sodium glycocholate (NaGC)-C₁₀E₈ have been studied on the basis of surface tensions, polarity of the micelle interior and the mean aggregation number. Application of two theoretical treatments, based on regular solution and excess thermodynamic quantities for critical micellar concentration (CMC) data from surface tension curves of two mixed systems showed that the mole fraction of each bile salt in the mixed micelles near the CMC is lower than that of the corresponding prepared mole fraction in the mixed solution. The polarity of the interior suggested that the hydrophobicity of intramicelles increased with the increase of the mole fraction of bile salt in the mixed solution and that the mixed micelles become dramatically more hydrophobic at a mole fraction of 0.68 for NaGC−C₁₀E₈ system and 0.75 for NaC−C₁₀E₈ system, respectively. This implies that the micelles become richer in the bile salt molecules and the tendency appears strongly for NaGC−C₁₀E₈ system due to the strong cohesion between the conjugated glycines in the NaGC molecules. The decrease of aggregation number with the increase of the mole fraction of bile salts shows that the micelles approach those of the single system of each bile salt. This supports the previously mentioned facts.     

Solubilization of unilamellar liposomes by betaine-type zwitterionic/anionic surfactant systems

The mechanisms governing the solubilizing interactions between zwitterionic/anionic mixed surfactant systems at different molar fractions of the zwitterionic surfactant (X_zwitter) and neutral or electrically charged unilamellar liposomes were investigated. The mixed systems were formed by N-dodecyl-N,N-dimethylbetaine and sodium dodecyl sulfate in the presence of piperazine-1,4-bis-(2-ethanesulfonic acid) buffer at pH 7.20. Unilamellar liposomes formed by egg phosphatidylcholine, in some cases together with stearylamine or phosphatidic acid, were used. Solubilization was detected as a decrease in static light-scattering of liposomes. Two parameters were regarded as corresponding to the effective surfactant/lipid molar ratios (Re) at which the surfactant system (i) saturated the liposomes, Re_sat, and (ii) led to a total solubilization of liposomes, Re_sol. From these parameters the bilayer/aqueous medium surfactant partition coefficients for the saturation (K_sat) and complete bilayer solubilization (K_sol) were determined. When X_zwitter was 0.40, The Re and K parameters showed a maximum, whereas the critical micellar concentration (CMC) of these systems exhibited a minimum, regardless of the electrical charge of bilayers. Given that the ability of the surfactant systems to saturate or solubilize liposomes is inversely related to the Re_sat and Re_sol parameters, these capacities appear to be directly correlated with the CMC of the mixed systems. The similarity of both K_sat and K_sol (particularly for X_zwitter=0.2–0.8) suggests that a similar partition equilibrium governs both the saturation and the complete solubilization of bilayers, the free surfactant concentration (S_a,S_b), remaining almost constant with similar values to the CMC for each mixed system studied.     

Micellization Behavior of Long-Chain Substituted Alkylguanidinium Surfactants

Surface activity and micelle formation of alkylguanidinium chlorides containing 10, 12, 14 and 16 carbon atoms in the hydrophobic tail were studied by combining conductivity and surface tension measurements with isothermal titration calorimetry. The purity of the resulting surfactants, their temperatures of Cr→LC and LC→I transitions, as well as their propensity of forming birefringent phases, were assessed based on the results of ¹H and ¹³C NMR, differential scanning calorimetry (DSC), and polarizing microscopy studies. Whenever possible, the resulting values of Krafft temperature (T_K), critical micelle concentration (CMC), minimum surface tension above the CMC, chloride counter-ion binding to the micelle, and the standard enthalpy of micelle formation per mole of surfactant (Δ_micH°) were compared to those characterizing alkyltrimethylammonium chlorides or bromides with the same tail lengths. The value of T_K ranged between 292 and 314 K and increased strongly with the increase in the chain length of the hydrophobic tail. Micellization was described as both entropy and enthalpy-driven. Based on the direct calorimetry measurements, the general trends in the CMC with the temperature, hydrophobic tail length, and NaCl addition were found to be similar to those of other types of cationic surfactants. The particularly exothermic character of micellization was ascribed to the hydrogen-binding capacity of the guanidinium head-group.     

A delicate ionizable-group effect on self-assembly and thermogelling of amphiphilic block copolymers in water

A carboxyl-capped PLGA-PEG-PLGA block copolymer (PLGA: poly(d,l-lactic acid-co-glycolic acid), PEG: poly(ethylene glycol)) was synthesized, and its self-assembly and thermogelling behaviors in water were studied at different pH values. While the aqueous solution of the virgin PLGA-PEG-PLGA block copolymer with the composition in this paper did not undergo sol-gel transition, that of the end-capped derivative exhibited four macroscopic states, sol, turbid sol, physical gel, and precipitate, dependent upon temperature and pH. Especially between pH 4.5 and 5.0, a concentrated aqueous system underwent sol-gel-(turbid sol)-precipitate transitions upon increase of temperature. Complex of dissociation constant pK_a of weak-acid groups on the micelle surfaces was illustrated. Dynamic light scattering, hydrophobic dye solubilization, transmission electron microscopy, NMR, and potentiometric titration were used to examine the relationship between ionization of the end groups of the polymer chains on the molecular level, micellization of the amphiphilic block copolymers on the supermolecular level, and physical gelation on the macroscopic level. The present research reveals the complex of the multi-scale self-assembly of amphiphilic polymer ionomers in a selective solvent.     

Polycyclic hydrocarbon and polychlorinated biphenyl solubilization in aqueous solutions of mixed micelles

To determine the physiochemical behavior of xenobiotic hydrocarbons in simulated intestinal content, we examined the partition of 7,12-dimethylbenzanthracene (DMBA), 3-methyl cholanthrene (MC), benzo(a)pyrene, and a polychlorinated biphenyl compound (PCB, Aroclor 1242) between an emulsified oil phase and a mixed micellar solution. In a mixed lipid-bile salt system, negligible amounts of hydrocarbon were present in aqueous solution below the critical micellar concentration (CMC) of sodium taurocholate. Once the CMC was obtained, the 4 hydrocarbons exhibited nearly identical partitions from the lipid into the micellar system which was enhanced by increased concentrations of bile salt, reduction of triglyceride concentration and the formation of mixed rather than pure bile salt micelles. The partition of DMBA and MC into micelles was optimized by long-chain monounsaturated oleic acid and monooleoylglycerol as compared to their octanoic or linoleic counterparts. Linoleic acid and monolinoleoylglycerol maximized the partition of PCB from the oil into the micellar phase. In a mixed micellar system excluding an oil phase and an excess of DMBA, a molar saturation ratio (mol hydrocarbon:mol bile salt) was calculated by regression analysis to be 0.162. This indicates that more than one molecule of hydrocarbon is solubilized per mixed micelle and that the aqueous solubilization of hydrocarbon may be attributed to true micellar solubilization.     

Solubilization of cholesterol in two binary mixed micelles of bile salt and nonionic surfactant

The saturated amounts of solubilized cholesterol (C_ch) in mixed micelles of sodium cholate (NaC) and octaoxy-ethylene glycol monon-decyl ether (C₁₀E₈) and of sodium zyme assay at 25, 29, 33 and 37°C. The C_ch values in both systems increase with the total surfactant concentration. Because the mixed micelles for both systems tend to form C₁₀E₈-rich micelles near the critical micellar concentration (CMC) of the mixed system, the curves of cholesterol solubility approached the C_ch curve for C₁₀E₈ alone near the CMC. The tendency of C_ch to decrease in both systems with increasing mole fractions of bile salts resembled that of the mean aggregation number of micelles. Thermodynamic analyses of cholesterol solubilization showed that the free energy of solubilization, if considered as the transfer of cholesterol from solid state to micellar environment, increased with increasing mole fraction of bile salt. The enthalpy of cholesterol solubilization (ΔH_S→M) decreased with the mole fraction of bile salts and showed break points around the mole fraction of 0.75 for the NaC−C₁₀E₈ system and at 0.60 for the NaDC−C₁₀E₈ system, respectively. These phenomena resemble earlier hydrophobicity data for mixed micelles by fluorescence measurements. Furthermore, C_ch values for the NaDC−C₁₀E₈ system were larger than those for the NaC−C₁₀E₈ system because of the structural differences at the 7α hydroxyl group between NaC and NaDC. This fact was confirmed by thermodynamic calculations.     

Double-Tailed Single-Head Amino Acid-Based Chiral Cationic Amphiphilic Molecules: Synthesis,Characterization, and Physicochemical Properties

Two double-tailed single-head amino acid-based chiral cationic amphiphilic molecules, l -aspartic acid hydrochloride dihexylester (L-ADHE, C₆–C₆) and l -aspartic acid hydrochloride dioctylester (L-ADOE, C₈–C₈), were synthesized. ¹H NMR, ¹³C NMR, and Fourier transform infrared (FT-IR) were used to characterize the structures of the esters. Micellization, surface, and structural properties of L-ADHE and L-ADOE in aqueous solution were studied by means of a number of techniques including conductivity, pH, surface tension, density, zeta potential, and dynamic light scattering (DLS). The critical micelle concentration (CMC) of L-ADHE and L-ADOE were found to be very low compared with those of corresponding single-tailed amino acid-based amphiphilic molecules. The pK_a values of L-ADHE and L-ADOE in aqueous solutions were determined via pH measurements, and it was observed that they had acidic properties giving low pK_a values. The excellent adsorption behaviors at the air/water interface of L-ADHE and L-ADOE in aqueous medium were obtained, i.e. they efficiently lowered the surface tension of water at CMC down approximately to 24.3 and 23.4 mN m⁻¹, respectively. From the density measurements, the volume change due to the micellization process for L-ADOE was found to be quite high compared to L-ADHE, i.e. about three times more. This result and the data obtained from the DLS revealed that the increase in aggregated structures of L-ADOE may be due to vesicle formation. The dye solubilization study was performed by UV–vis absorption spectroscopy for L-ADHE. Besides, the CMC value of L-ADHE was also successfully determined without using any dye through UV–vis spectroscopy.     

Salt‐Induced Modulation of the Krafft Temperature and Critical Micelle Concentration of Benzyldimethylhexadecylammonium Chloride

In this work, the effect of some sodium salts on the Krafft temperature (T_K) and critical micelle concentration (CMC) of benzyldimethylhexadecylammonium chloride (C16Cl) in aqueous solution has been studied. It was observed that the T_K can be modulated to lower and higher values and the CMC can be depressed significantly upon the addition of the electrolytes. More chaotropic Br^? and I^? raise the T_K with an increase of the concentration of the ions. On the other hand, less chaotropic NO₃^? initially lowers and then raises the T_K. Kosmotropic F^?, SO₄^2? and CO₃^2? gradually lower the T_K with increasing concentration of the electrolytes. The more chaotropic ions form contact ion pairs with the surfactant and decrease the solubility with a consequent increase in the T_K. On the other hand, kosmotropic ions, being extensively hydrated in the bulk, remain separated from the surfactant by hydrated layers of water molecules. As a result, a significant electrostatic repulsion exists between the charged headgroups of the surfactant, resulting in a decrease in the T_K. The CMC of the surfactant decreases significantly in the presence of these ions. The surface tension at the CMC (γ_CMC) also decreases in the presence of all the salts except for F^?. The electrostatic repulsion between the charged headgroups is significantly reduced because of screening of the surface charge of both micelles and adsorbed monolayers by the associated counterions, resulting in a decrease in both the CMC and γ_CMC.     

Study of Solubility Efficiency of Polycyclic Aromatic Hydrocarbons in Single Surfactant Systems

Water solubility enhancements of two polycyclic aromatic hydrocarbons i.e., naphthalene (Naph) and anthracene (Anth) in single surfactants system have been measured by UV–VIS-Spectrophotometer. The relationships between solubilizing capacity and their solubilization efficiency towards polycyclic aromatic hydrocarbons (PAH) have been quantified and discussed in terms of the molar solubilization ratio (MSR), the micelle-water partition coefficient (K _m) and standard free energy of solubilization (ΔG°_s). The micellar and surface properties of some cationic and anionic surfactants have been investigated by conductivity, surface tension and fluorescence measurements at 300 K. Above the CMC, maximum solubilization occurs in cationic surfactants where as the solubilization is least in the presence of anionic surfactants. The negative value of ΔG°_s shows spontaneity of the solubilization process. The MSR values are larger in naphthalene than anthracene (Naph > Anth). The present studies provide valuable information for the selection of surfactants for solubilizing water-insoluble compounds.     

Mixed Micellization Study of Alkyltrimethylammonium and Alkyltriphenylphosphonium Bromides in Aqueous Solution

Mixed micellization study of cationic surfactants viz. alkyltrimethylammonium bromides (C_nTAB) and alkyltriphenylphosphonium bromides (C_nTPPB) with similar hydrophobic groups (C₁₂-, C₁₄-, and C₁₆-) was performed using tensiometry and UV–visible light spectrophotometry techniques. Critical micelle concentration (CMC) values of the single and binary surfactant mixtures were obtained from a plot of surface tension versus the logarithm of surfactant concentration (C _s). The degree of synergy and various mixed micelle parameters like interaction parameter (β), activity coefficients (f ^m ) and interfacial parameters like surface pressure (π _CMC), packing parameter (P), surface excess concentration (Г _max), surface tension at the CMC (γ _CMC), and minimum area per molecule (A _min) were evaluated using the regular solution theory (RST). Thermodynamic parameters were calculated using several proposed models which suggest the mixed micellar system to be more thermodynamically stable than their respective individual components. In addition, a dye solubilization study was performed using a spectrophotometric method to validate the CMC data obtained from tensiometric method. Conductometric measurements were also carried out for the mixture of C₁₂TAB + C₁₂TPPB only as it showed a more negative β, indicating a higher degree of synergism.     

The energetics of micellar solubilization

Micellar solubilization, an action of the detergency mechanism, is considered from the stand-point of quasi-thermodynamics. The basis of the approach was suggested by the similarity of micellar solubilization and Freundlich adsorption isotherms. Free energy change (ΔG), heat of solubilization (ΔH) and change in entropy (ΔS) for the micellar solubilization of Orange OT are calculated using two-phase theory and the Gibbs-Helmholtz equation. It is postulated that the dye concn in the solution (monomer) phase is that at the critical micelle concn. The dye concn in the solubilized phase is computed for the dye-penetrated portion of the micellar volume. Calculated values of ΔG in anionic and nonionic surfactants are of the order of magnitude of a physical adsorption. The positive ΔH values indicate the process is not an adsorption. The positive ΔS values point to increased randomness or possibly to decreased energy effects due to iceberg water molecule structure surrounding the hydrophobic dye molecules. The loss of the water structure around the latter in the solubilization process would result in their acquiring increased configu-rational entropy.