Search Results (50)

In this study, a quantitative profiling method for detecting free fatty acids in crude lanolin based on the Quality by Design (QbD) concept was developed. High-performance liquid chromatography (HPLC) equipped with a charged aerosol detector (CAD) and a Proshell 120 EC C18 column was employed for the separation of crude lanolin components. Initially, the analytical target profile and critical method attributes were defined. Potential critical method parameters, including column temperature, flow rate, isocratic run time, gradient end organic phase ratio, and gradient time, were identified using fishbone diagrams and single-factor experiments. The definitive screening design (DSD) was then utilized to screen and optimize these parameters. Stepwise regression was applied to establish quantitative models between the critical method attributes and the method parameters. Subsequently, the method operable design region (MODR) was calculated and was successfully verified. The analytical conditions established were configured with 0.1% formic acid in water and 0.1% formic acid in acetonitrile serving as the mobile phases. The flow rate was set at 0.8 mL/min, and the column temperature was maintained at 35 °C with the evaporation tube temperature also set at 35 °C. An injection volume of 10 μL was used for each analysis. The gradient elution conditions were as follows: from 0 to 30 min, 75% of solvent B was used, and from 30 to 60 min, the proportion of solvent B was increased from 75% to 79%. Ten components, including 12-hydroxystearic acid, 2-hexyldecanoic acid, and palmitic acid, were identified by mass spectrometry, and seven common peaks were found in the fingerprints. The contents of palmitic acid, oleic acid, and stearic acid in the crude lanolin were quantitatively determined. Both the fingerprint and quantitative analysis methods were validated. The method was applied to analyze 15 batches of crude lanolin from different sources. The new established quantitative profiling method for free fatty acids can be potentially used for industrial applications to enhance the quality control of crude lanolin. Full article

In the field of medicinal chemistry, the introduction of silylated groups is an important strategy to alter the activity, selectivity, and pharmacokinetics of compounds based on the diverse traits of silicon, including atomic size, electronegativity, and hydrophobicity. The hydroxy group on C-9 or C-9 and C-10 of hydroxystearic acids have been functionalized as t-butyl dimethyl silyl ether. The target compounds have been fully characterized and tested for in vitro cytotoxicity in tumor cells HT29, HCT116, CaCo2, HeLa, MCF7, U2OS, and Jurkat J6 and normal I407 cells. In particular, the silyl derivative of (R)-9-hydroxystearic acid was more active in colon cancer cells. Analyses of cell proliferation, oxidative cell status, histones post-translational modifications, protein phosphorylation, gene expression, and DNA damage were performed to obtain information on the antitumor properties of the new molecules in comparison with the unmodified (R)-9-hydroxystearic acid’s previously studied effects. Our results suggest that the incorporation of a silyl functionality may be a useful tool for the structural development of new pharmaceutically active compounds against colon cancer. Full article

Breast milk is a rich source of fatty acids (FAs) while being irreplaceable for the health and development of an infant. Herein, we present a fast and simple method for the direct detection and quantification of 37 free FAs (FFAs) in breast milk samples, avoiding any derivatization step, and a study on the % variation of FA contents in samples collected from the same mother within five consecutive days. The average breakdown of FAs was 60.5% saturated and 39.5% unsaturated, in which polyunsaturated FAs were 13.3% and monounsaturated FAs 26.2%. The most abundant FFA in the breast milk samples was C12:0 (18.3%), followed by C10:0 (15.0%), suggesting that further attention must be paid to the presence and role of medium-chain FAs. Among unsaturated FAs, oleic acid (C18:1 n-9) (13.3%) and linoleic acid (C18:2 n-6) (10.1%) were the most abundant. Remarkable variations of FFA contents within the five consecutive days were observed for C8:0, C10:0, C12:0, C18:1 n-9, and C18:2 n-6. The two isomers α-linolenic acid (C18:3 n-3) and γ-linolenic acid (C18:3 n-6) were quantified in all breast milk samples. The ratio of γ-linolenic acid, which most recently is important for cardiac metabolic maturation, to α-linolenic acid was found to be 1:2. Most importantly, in the present study, we explored the presence of bioactive saturated monohydroxy fatty acids (SHFAs), demonstrating for the first time the existence of distinct hydroxypalmitic and hydroxystearic acids (HPAs and HSAs, respectively) in breast milk. Full article

Organogels are semi-solid pharmaceutical forms whose dispersing phase is an organic liquid, for example, an oil, such as acai oil, immobilized by a three-dimensional network formed by the gelling agent. Organogels are being highlighted as innovative release systems for cosmetic active ingredients such as hyaluronic acid for topical applications. Acai oil was evaluated for its physicochemical parameters, fatty acid composition, lipid quality index, spectroscopic pattern (Attenuated total reflectance Fourier Transform Infrared Spectroscopy), thermal behavior, total phenolic, total flavonoids, and total carotenoids and β-carotene content. The effectiveness of the organogel incorporated with hyaluronic acid (OG + HA) was evaluated through ex vivo permeation and skin retention tests, in vitro tests by Attenuated total reflectance Fourier Transform Infrared Spectroscopy and Differential Scanning Calorimetry. The physicochemical analyses highlighted that the acai oil exhibited quality standards in agreement with the regulatory bodies. Acai oil also showed high antioxidant capacity, which was correlated with the identified bioactive compounds. The cytotoxicity tests demonstrated that the formulation OG + HA does not release toxic substances into the biological environment that could impede cell growth, adhesion, and efficacy. In vitro and ex vivo analyses demonstrated that after 6 h of application, OG + HA presented a high level of hydration, thermal protection and release of HA. Thus, it can be concluded that the OG + HA formulation has the potential for physical–chemical applications, antioxidant quality, and potentially promising efficacy for application in the cosmetic areas. Full article

Chemiluminescence in solution-based systems has been extensively studied for the chemical analysis of biomolecules. However, investigations into the control of chemiluminescence reactions in gel-based systems, which offer flexibility in reaction conditions (such as the softness of the reaction environment), have only recently begun in polymer materials, with limited exploration in low-molecular-weight gelator (LMWG) systems. In this study, we investigated the chemiluminescence behaviors in the gel states using LMWG systems and evaluated their applicability to fluorescent-dye-containing molecular organogel systems/oxidant-containing aqueous systems. Using diethyl succinate organogels composed of 12-hydroxystearic acid as a molecular organogelator, we examined the fluorescent properties of various fluorescent dyes mixed with oxidant aqueous solutions. As the reaction medium transitioned from the solution to the gel state, the emission color and chemiluminescence duration changed significantly, and distinct characteristics were observed, for each dye. This result indicates that the chemiluminescence behavior differs significantly between the solution and gel states. Additionally, visual inspection and dynamic viscoelastic measurements of the mixed fluorescent dye-containing molecular gels and oxidant-containing aqueous solutions confirmed that the chemiluminescence induced by the mixing occurred within the gel phase. Furthermore, the transition from the solution to the gel state may allow for the modulation of the mixing degree, thereby enabling control over the progression of the chemiluminescence reaction. Full article

In this work, a detailed analysis of the lipid component in primary sludge and sewage scum up-taken from several wastewater treatment plants located in southern Italy was carried out. Lipids in the primary sludge accounted for 200–250 mg/g of the total solids (TS), with calcium soaps as a main component (70–82%), while total lipids made up about 350–500 mg/g_TS in the sewage scum and consisted mainly of FFAs (45–60%) and calcium soaps (27–35%). In addition, estolides and 10-hydroxystearic acid were also quantified. A specific valorization process was then developed and tested for either primary sludge or sewage scum. In detail, lipids were first recovered, chemically activated by the addition of acids (calcium soaps were converted to free fatty acids) and finally reacted with methanol to obtain methyl esters. The lipid recovery from primary sludge and sewage scum was particularly efficient (recoverability of 92–99%). The conversion of the starting acids into FAMEs (yield > 98%) was achieved under very mild conditions (70 °C, 2 h) with AlCl₃·6H₂O as a catalyst. Biodiesel (according to EN14214), methyl 10-hydroxystearate and methyl estolides were efficiently isolated by distillation under vacuum. Finally, a feasibility study of the proposed processes was carried out to evaluate their possible integration into a wastewater treatment plant, critically analyzing both the positive aspects and the relative limitations. Full article

Sulfonic resins can replace homogeneous sulfonic acids in the oxidation of alcohols with the H₂O₂/KBr system. The performance of different resins was tested with methyl 9(10)-hydroxystearate, a secondary fatty alcohol. The structural features of the resin were more important than the acid strength for the catalytic performance of this reaction. The optimization of the reaction conditions allows the recovery of the resin, although regeneration is required due to the active role of KBr, and a significant loss of sulfonic groups can be detected after nine runs. In the case of primary fatty alcohols, the oxidation leads to carboxylic acids, which are esterified with the starting alcohol under the acidic conditions. For cyclic secondary alcohols, the steric hindrance around the hydroxyl group seems to be important for the efficiency of the oxidation to ketone. Full article

Hydroxy fatty acids (HFAs) constitute a class of lipids, distinguished by the presence of a hydroxyl on a long aliphatic chain. This study aims to expand our insights into HFA bioactivities, while also introducing new methods for asymmetrically synthesizing unsaturated and saturated HFAs. Simultaneously, a procedure previously established by us was adapted to generate new HFA regioisomers. An organocatalytic step was employed for the synthesis of chiral terminal epoxides, which either by alkynylation or by Grignard reagents resulted in unsaturated or saturated chiral secondary alcohols and, ultimately, HFAs. 7-(S)-Hydroxyoleic acid (7SHOA), 7-(S)-hydroxypalmitoleic acid (7SHPOA) and 7-(R)- and (S)-hydroxymargaric acids (7HMAs) were synthesized for the first time and, together with regioisomers of (R)- and (S)-hydroxypalmitic acids (HPAs) and hydroxystearic acids (HSAs), whose biological activity has not been tested so far, were studied for their antiproliferative activities. The unsaturation of the long chain, as well as an odd-numbered (C17) fatty acid chain, led to reduced activity, while the new 6-(S)-HPA regioisomer was identified as exhibiting potent antiproliferative activity in A549 cells. 6SHPA induced acetylation of histone 3 in A549 cells, without affecting acetylated α-tubulin levels, suggesting the selective inhibition of histone deacetylase (HDAC) class I enzymes, and was found to inhibit signal transducer and activator of transcription 3 (STAT3) expression. Full article

Thickener, also known as a gelling agent, is a critical component of lubricating greases. The most critical property of thickener, temperature resistance, is determined by the molecular structure of the compounds. Currently, all high-temperature-resistant thickeners are based on 12-hydroxystearic acid, which is exclusively produced from castor oil. Since castor oil is also an important reagent for other processes, finding a sustainable alternative to 12-hydroxystearic acid has significant economic implications. This study synthesises an alternative thickener from abundant agricultural waste, cashew nut shell liquor (CNSL). The synthesis and separation procedure contains three steps: (i) forming and separating calcium anacardate by precipitation, (ii) forming and separating anacardic acid (iii) forming lithium anacardate. The obtained lithium anacardate can be used as a thickener for lubricating grease. It was found that the recovery of anacardic acid was around 80%. The optimal reaction temperature and time conditions for lithium anacardate were 100 °C and 1 h, respectively. The method provides an economical alternative to castor and other vegetable oils. The procedure presents a simple pathway to produce the precursor for the lubricating grease from agricultural waste. The first reaction step can be combined with the existing distillation of cashew nut shell processing. An effective application can promote CNSL to a sustainable feedstock for green chemistry. The process can also be combined with recycled lithium from the spent batteries to improve the sustainability of the battery industry. Full article

Lipid reprogramming metabolism is crucial for supporting tumor growth in breast cancer and investigating potential tumor biomarkers. Fatty acid esters of hydroxy fatty acids (FAHFAs) are a class of endogenous lipid metabolites with anti-diabetic and anti-inflammatory properties that have been discovered in recent years. Our previous targeted analysis of sera from breast cancer patients revealed a significant down-regulation of several FAHFAs. In this study, we aimed to further explore the relationship between FAHFAs and breast cancer by employing chemical isotope labeling combined with liquid chromatography−mass spectrometry (CIL-LC-MS) for profiling of FAHFAs in tumors and adjacent normal tissues from breast cancer patients. Statistical analysis identified 13 altered isomers in breast cancer. These isomers showed the potential to distinguish breast cancer tissues with an area under the curve (AUC) value above 0.9 in a multivariate receiver operating curve model. Furthermore, the observation of up-regulated 9-oleic acid ester of hydroxy stearic acid (9-OAHSA) and down-regulated 9-hydroxystearic acid (9-HSA) in tumors suggests that breast cancer shares similarities with colorectal cancer, and their potential mechanism is to attenuate the effects of pro-apoptotic 9-HSA by enhancing the synthesis of FAHFAs, thereby promoting tumor survival and progression through this buffering system. Full article

This study examines the structures of soft surfactant-based biomaterials which can be tuned by temperature. More precisely, investigated here is the behavior of stearic acid (SA) and 12-hydroxystearic acid (12-HSA) aqueous mixtures as a function of temperature and the 12-HSA/SA molar ratio (R). Whatever R is, the system exhibits a morphological transition at a given threshold temperature, from multilamellar self-assemblies at low temperature to small micelles at high temperature, as shown by a combination of transmittance measurements, Wide Angle X-ray diffraction (WAXS), small angle neutron scattering (SANS), and differential scanning calorimetry (DSC) experiments. The precise determination of the threshold temperature, which ranges between 20 °C and 50 °C depending on R, allows for the construction of the whole phase diagram of the system as a function of R. At high temperature, the micelles that are formed are oblate for pure SA solutions (R = 0) and prolate for pure 12-HSA solutions (R = 1). In the case of mixtures, there is a progressive continuous transition from oblate to prolate shapes when increasing R, with micelles that are almost purely spherical for R = 0.33. Full article

False brinelling damage in rolling bearings can lead to reduced component lifetimes and increased noise emissions, adversely affecting machine performance. Therefore, minimizing or avoiding such damage is very important. Environmental or operating conditions that can lead to false brinelling damage often cannot be avoided. Alternatively, such damage can be significantly reduced with suitable lubricants. This study utilized a test method from the research project FVA 540 to examine the impact of the base oil viscosity and NLGI class of greases on false brinelling damage at different temperatures. The results showed a clear dependency between the base oil viscosity of greases and the extent of false brinelling damage. Two different thickeners (lithium hydroxystearate/diurea) and different base oil types (PAO/esters) were investigated for this purpose. The results indicate that temperature had a significant effect on the physical and rheological properties of greases and show the potential for reducing false brinelling damage through the selection of appropriate lubricants. These results provide valuable information to improve the performance and lifetime of rolling bearings in industrial settings. Full article

Here, we describe the behavior of mixtures of stearic acid (SA) and its hydroxylated counterpart 12-hydroxystearic acid (12-HSA) in aqueous mixtures at room temperature as a function of the 12-HSA/SA mole ratio R. The morphologies of the self-assembled aggregates are obtained through a multi-structural approach that combines confocal and cryo-TEM microscopies with small-angle neutron scattering (SANS) and wide-angle X-ray scattering (WAXS) measurements, coupled with rheology measurements. Fatty acids are solubilized by an excess of ethanolamine counterions, so that their heads are negatively charged. A clear trend towards partitioning between the two types of fatty acids is observed, presumably driven by the favorable formation of a H-bond network between hydroxyl OH function on the 12th carbon. For all R, the self-assembled structures are locally lamellar, with bilayers composed of crystallized and strongly interdigitated fatty acids. At high R, multilamellar tubes are formed. The doping via a low amount of SA molecules slightly modifies the dimensions of the tubes and decreases the bilayer rigidity. The solutions have a gel-like behavior. At intermediate R, tubes coexist in solution with helical ribbons. At low R, local partitioning also occurs, and the architecture of the self-assemblies associates the two morphologies of the pure fatty acids systems: they are faceted objects with planar domains enriched in SA molecules, capped with curved domains enriched in 12-HSA molecules. The rigidity of the bilayers is strongly increased, as well their storage modulus. The solutions remain, however, viscous fluids in this regime. Full article

Currently, there is renewed interest in using fatty acid soaps as surfactants. Hydroxylated fatty acids are specific fatty acids with a hydroxyl group in the alkyl chain, giving rise to chirality and specific surfactant properties. The most famous hydroxylated fatty acid is 12-hydroxystearic acid (12-HSA), which is widely used in industry and comes from castor oil. A very similar and new hydroxylated fatty acid, 10-hydroxystearic acid (10-HSA), can be easily obtained from oleic acid by using microorganisms. Here, we studied for the first time the self-assembly and foaming properties of R-10-HSA soap in an aqueous solution. A multiscale approach was used by combining microscopy techniques, small-angle neutron scattering, wide-angle X-ray scattering, rheology experiments, and surface tension measurements as a function of temperature. The behavior of R-10-HSA was systematically compared with that of 12-HSA soap. Although multilamellar micron-sized tubes were observed for both R-10-HSA and 12-HSA, the structure of the self-assemblies at the nanoscale was different, which is probably due to the fact that the 12-HSA solutions were racemic mixtures, while the 10-HSA solutions were obtained from a pure R enantiomer. We also demonstrated that stable foams based on R-10-HSA soap can be used for cleaning applications, by studying spore removal on model surfaces in static conditions via foam imbibition. Full article

The Hansen solubility parameter (HSP) is a useful index for reasoning the gelation behavior of low-molecular-weight gelators (LMWGs). However, the conventional HSP-based methods only “classify” solvents that can and cannot form gels and require many trials to achieve this. For engineering purposes, quantitative estimation of gel properties using the HSP is highly desired. In this study, we measured critical gelation concentrations based on three distinct definitions, mechanical strength, and light transmittance of organogels prepared with 12-hydroxystearic acid (12HSA) and correlated them with the HSP of solvents. The results demonstrated that the mechanical strength, in particular, strongly correlated with the distance of 12HSA and solvent in the HSP space. Additionally, the results indicated that the constant volume-based concentration should be used when comparing the properties of organogels to a different solvent. These findings are helpful in efficiently determining the gelation sphere of new LMWGs in HSP space and contribute to designing organogels with tunable physical properties. Full article