BEHENYL ALCOHOL

In oleogel food systems (based on the mixture between stearic acid and stearyl alcohol) the strong effect of the weight ratio (R) between these two components on the textural and structural properties is well described. The effect of R for other fatty acids and fatty alcohols is less explored. Moreover, they do not show an enhancement of the oleogel properties for specific R. The effect of R on the oleogel properties, for a mixture of fatty acid and fatty alcohol with longer alkyl chains (behenyl alcohol and behenic acid) in sunflower and soybean oils, which are raw materials widely used in cosmetic and pharmaceutical industries, was investigated. We characterized the oleogel properties as a function of R in terms of structuring potential: hardness, oil loss and gel stability. This information was correlated with microstructural data obtained at different length scales by coupling optical microscopy, DSC, SFC, SAXS and WAXS experiments. Our results highlight that R tunes the oleogel properties in a comparable manner to previous results obtained for stearic acid and stearyl alcohol-based oleogels. Two specific R (8:2 and 7:3) close to the 3:1 molecular ratio gave oleogels with both the highest hardness and stability. The morphology and size of the mixed crystals obtained for these R cannot solely explain why they are stronger gels with low oil loss in comparison to the other R. The almost complete crystallization for these two R is one of the key parameters controlling the oleogel properties. As described in the literature, we also suggest that the differences in oleogel properties come from the spatial distribution of the crystalline mass. In this study, we confirm that the effect of the 3:1 molecular ratio in mixed surfactant systems described more than 50 years ago for foams, emulsions and Langmuir monolayers occurs also on the crystallization of mixed fatty alcohol and fatty acid in oils leading to better oleogels properties.

Recently, we described that the weight ratio ( R ) between behenyl alcohol (BO) and behenic acid (BA) in sunflower oil effects the textural and structural properties of the oleogel system. One R (7:3) was found as optimal since it led to an enhancement of the oleogel properties for both the hardness and the stability in terms of oil-binding capacity. However, what remains unknown is the effect of other vegetable oils. Therefore, in this study, we aim to test a range of different vegetable oils that are widely used in the cosmetic industry. All the oleogels were prepared by heating together at 85°C the oil and the fatty components under magnetic stirring. After heating, the samples were allowed to cool down quiescently to room temperature without any stirring. The oil properties tested included viscosity, density, and surface tension. The oleogel properties (hardness, oil loss, and gel stability) and their structure as a function of R were characterized at different length scales by coupling optical microscopy, differential scanning calorimetry (DSC), Small-Angle X-ray Scattering (SAXS), and Wide-Angle X-ray Scattering (WAXS) experiments. The same crystal structure evolution determined by SAXS and WAXS as a function of R was observed whatever the oil. In the DSC profiles and optical microscopy pictures, no oil effect was detected. However, our results highlighted two different optimal ratios, giving rise to the best oleogels in terms of stability (oil loss) and hardness as a function of the oil. For sunflower, apricot, and rapeseed oils, R = 7:3 was the optimal ratio, whereas R = 8:2 was the optimal ratio for olive and camelina oil. These observations were correlated with the fatty acid chain length composition of the oil. The results obtained have practical applications for the cosmetic industry since it establishes formulation rules for oleogel systems. Oleogels are based on BO and BA components, which are raw materials widely used for hair and skin applications.Different oils have different fatty acid chain lengths composition and as a result, the ratio between BO and BA needs to be adjusted in order to obtain the best oleogel in terms of texture and stability, which can then be used also to produce oil foams.

The focus of this communication was to study phospholipid-structured emulsions whose phase behaviour is modified with monoalkyl fatty amphiphiles. Ideally, these systems would mimic key physical and structural attributes observed in human stratum corneum (SC) so that they better alleviate xerotic skin conditions. Phosphatidylcholine-structured emulsions were prepared, and their phase behaviour modified with monoalkyl fatty amphiphiles. The effect of molecular volume, acyl chain length and head-group interactions was studied using a combination of physical methods. Water vapour transmission rate (WVTR) was used as a primary test to assess occlusive character. Changes in the vibrational modes observed in Fourier transform infrared (FTIR) spectroscopy and bilayer spacing measured by X-ray diffraction (XRD) were then applied to elucidate the lateral and lamellar microstructural characteristics in the systems. Water vapour transmission rate demonstrated that as the phosphatidylcholine acyl chain length increased from C14, to C18, to C22, there was a corresponding increase in occlusive character. The addition of monoalkyl fatty amphiphiles such as behenic acid, behenyl alcohol or cetostearyl alcohol to a base formulation incorporating dipalmitoyl and distearoylphosphatidylcholine (C18) was seen to further increase barrier characteristics of the emulsions. FTIR methods used to probe lipid-chain conformational ordering demonstrated that as phosphatidylcholine acyl chain lengths increased, there was a corresponding improvement in acyl chain ordering, with an increase in thermal transition temperatures. The addition of a monoalkyl fatty amphiphile resulted in conformational order and thermal transition temperature improvements trending towards those observed in stratum corneum. FTIR also demonstrated that systems containing behenic acid or behenyl alcohol exhibited features associated with orthorhombic character. X-ray diffraction data showed that addition of monoalkyl fatty amphiphile also resulted in thicker lamellar structures than when those agents are not present. The generalized approach described herein is shown to mechanistically describe the occlusive character of phospholipid-structured formulations in the presence of long-chain fatty acids or alcohols and that they exhibit characteristics mimicking those found in human SC lipids.

In recent years, hair coloring gains popularity as a trend of consumer's hair care. This coloring frequently damages hair. In response to this, a new shampoo-base was developed for repairing hair damaged by coloring. The new shampoo-base was prepared by dispersing cationic assembly in a solution of amphoteric surfactants. The mixture of behenyl trimethyl ammonium chloride (C22TAC) and behenyl alcohol (C22OH) was applied as the cationic assembly, which are dispersed in amido propyl betaine laurate (LPB) solution. LPB, which behaves as an amphoteric surfactant, was used as the wash-base. It was verified from the results on the measurements of DSC, calorimeter polarization, cryo-SEM and X-ray diffraction that the cationic assembly has a crystalline structure in the LPB solution. The new shampoo-base was highly efficient to change the color-damaged hair from hydrophilic to hydrophobic. The friction level of the hair washed with the new shampoo-base recovered to the same state as that of healthy hair. The exfoliation of cuticle was reduced after washing with the new shampoo-base.

An amino acid surfactant, monosodium N-stearoyl-L-glutamate (MSSG), was assumed to associate with higher alcohols (HAs) in 1:1 molar ratio in an aqueous phase, and the packing parameters of the 1/1 MSSG/HA associates, Pa, were calculated by molecular dynamics (MD). Pa is defined as At1(l(t1)+l(t2))/a(h)l(t1), where At1 stands for the cross-sectional area of the MSSG tail, l(t1) for the length of the MSSG tail, l(t2) for the length of the HA tail, and a(h) for the area of the MSSG head group. The Pa value increased from 0.83 to 1.02 as the HA tail length (l(t2)) increased from C14 to C22. Associates of HAs having longer tails with MSSG are likely to fit better into bilayers because Pa is closer to 1 when l(t2) is longer. In the graphical results of the MD simulation for the association, however, a steric hindrance was found between the head groups of MSSG/HA when l(t2) was > or = C19. Based on this result, HA was classified into short-chain HA (SCHA, l(t2) < C19) and long-chain HA (LCHA, l(t2) > or = C19), and several possible packing units, composed of compositional combinations of MSSG, SCHA, and LCHA, were proposed. The packing unit is a building block which could constitute bilayers, and it is composed of variable compositional combinations of MSSG/HA. Assuming that SCHA associates with MSSG, the packing parameter, Punit, was calculated in a water box by MD for each packing unit. Punit is the packing parameter of a packing unit and it is defined as Vu/l(u)a(u), where Vu is the tail volume of the packing unit, l(u) is the chain length, and a(u) is the head area. For the calculation, stearyl alcohol (C18-OH, SA) was chosen as a SCHA and behenyl alcohol (C22-OH, BA) as a LCHA. When the compositional ratio MSSG:SCHA:LCHA was 1:1:1, Punit was around 1. The packing unit having Punit of around 1 formed a colloidally stable suspension for 30 days and its aggregate was a lamellar structure. However, the other packing units, for which Punit deviates significantly from 1, precipitated out in their suspensions and showed no evidence of a lamellar structure. According to the graphical MD simulations for the compositional MSSG/SCHA/LCHA associations in bilayers, vertical steric hindrance was found between LCHAs when Punit deviated significantly from 1. The steric hindrance would prevent the packing units from forming a stable bilayer and induce precipitation in the suspensions. Therefore, a proper combinational ratio of MSSG:LCHA:SCHA would play a major role in forming a lamellar structure.

Candelilla wax (CW) is used as an oil-gelling agent in cosmetic sticks. However, its hardness is inadequate compared to those of hydrocarbon waxes such as paraffin. In this study, behenyl behenate (BB), an additive plant-derived wax ester with a high melting point, was shown to improve the oil-gel hardness of CW.Although the gel with BB alone had a relatively low gel hardness, when BB was mixed with CW at a ratio of 70:30 (CW:BB), the gel hardness significantly increased to four times that of the CW gel. The hardness of the CW and BB mixtures was higher than that of paraffin wax, which is used to solidify cosmetic oils. An increase in gel hardness was not observed when additives with chemical structures similar to those of BB, such as stearyl stearate (which has a lower molecular weight than BB) and behenic acid or behenyl alcohol (which are components of BB), were blended.Scanning electron microscopy indicated the presence of many spherical clusters comprising fine crystallites in the CW gel. This morphology was in contrast to that of paraffin wax gel, in which only plate crystals were observed. It was concluded that this heterogeneous structure led to the low gel hardness of CW. When BB was added to CW, the spherical clusters disappeared, and the internal structure changed to a homogeneous card-house structure composed of plate crystals.