Polymer-Fish oil bigel (hydrogel/oleogel colloidal mixture) was developed by using fish oil and natural (sodium alginate) and synthetic (hydroxypropyl methylcellulose) polymer for pharmaceutical purposes. The bigels were closely monitored and thermal, rheological and mechanical properties were compared with the conventional hydrogels for their potential use as an effective transdermal drug delivery vehicle. Stability of the fish oil fatty acids (especially eicosapentanoic acid, EPA and docosahexanoic acid, DHA) was determined by gas chromatography and the drug content (imiquimod) was assessed with liquid chromatography. Furthermore, in vitro permeation study was conducted to determine the capability of the fish oil-bigels as transdermal drug delivery vehicle. The bigels showed pseudoplastic rheological features, with excellent mechanical properties (adhesiveness, peak stress and hardness), which indicated their excellent spreadability for application on the skin. Bigels prepared with mixture of sodium alginate and fish oil (SB1 and SB2), and the bigels prepared with the mixture of hydroxypropyl methylcellulose and fish oil (HB1-HB3) showed high cumulative permeation and drug flux compared to hydrogels. Addition of fish oil proved to be beneficial in increasing the drug permeation and the results were statistically significant (p < 0.05, one-way Anova, SPSS 20.0). Thus, it can be concluded that bigel formulations could be used as an effective topical and transdermal drug delivery vehicle for pharmaceutical purposes.
Volatile oils obtained from both the liquid medium after incubation (MAI) and liquid medium before incubation (MBI) in the cultivation process of Lactobacillus acidophilus were isolated by hydrodistillation (HD) and analyzed to investigate the utility of the liquid waste. The composition of the volatile oils was analyzed by capillary gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). In total, 46 and 19 compounds were detected in the volatile oils from MAI (MAI oil) and MBI (MBI oil), respectively. The principle components of MAI oil were fatty acids, including pentanoic acid (12.75%), heptanoic acid (14.05%), and nonanoic acid (14.04%). The important aroma-active compounds in the oils were detected by GC-MS/Olfactometry (GC-O), and their intensity of aroma were measured by aroma extraction dilution analysis (AEDA). Pyrazines were determined as key aroma components; in particular, 2-ethyl-5-methylpyrazine was the most primary aroma-active compound in MAI oil. In addition, as the characteristic aroma-active compounds, 3-(methylthio)-propanal, trimethylpyrazine, and pentanoic acid were also detected in MAI oil. These results imply that the waste medium after incubation of L. acidophilus may be utilized as a source of volatile oils.
The effects on lipid metabolism of four different n-3 highly unsaturated fatty acids (n-3HUFA) including eicosapentaenoic acid (EPA, 20:5n-3), docosapentaenoic acid (DPA, 22:5n-3), docosahexaenoic acid (DHA, 22:6n-3), and tetracosahexaenoic acid (THA, 24:6n-3) were compared in the HepG2 cell model. None of the n-3HUFAs affected the viability of the cells. THA exerted the strongest suppression on the synthesis of triacylglycerol and cholesteryl ester (ChE), and the order of the strength of suppression was found to be THA > DHA > DPA > EPA. The mRNA level of fatty acid synthase was suppressed by the n-3HUFAs and the order of the strength of suppression by n-3HUFAs was the same in both triacylglycerol and ChE synthesis. These findings support previous animal test results using EPA, DPA, and DHA. In conclusion, both the number of carbon atoms and double bonds in an n-3HUFA structure has an effect on lipid metabolism in HepG2 cells.
It has been reported that polydimethylsiloxane (PDMS) inhibits oxygen dissolution into oil by forming a monolayer on the surface of the oil, thereby reducing thermal oxidation. In the present study, the distribution of PDMS was determined by the inductively coupled plasma atomic emission spectroscopy in standing PDMS-containing canola oil. PDMS did not disperse in the oil uniformly, but there was a tendency that the PDMS concentration decreased as the depth of oil increased, and the concentration of the bottom part was the lowest. When canola oil was covered with PDMS by dropping it gently on the surface of the oil and kept at 60°C, the oxygen content and oxidation of the oil were lower than those of the control canola oil. PDMS-containing canola oil and canola oil were heated with stirring from room temperature to 180°C, and then allowed to stand while cooling. Oxygen contents of both oils increased up to 120°C then dropped abruptly. While cooling, oxygen contents sharply increased at 100°C and approached the saturation content, although the increase for PDMS-containing canola oil was a little slow. Likewise, the thermal treatment of PDMS-containing canola oil and canola oil at 180°C for 1 h under stirring was repeated 5 times with standing intervals for 2-3 days at room temperature. Oxidation of the former was less than that of the latter in spite of its high oxygen content. In conclusion, the oxygen content of oil with/without PDMS addition increased, but oxidation of PDMS-containing canola oil was inhibited both during heating and standing with intermittent heating. It was suggested that PDMS exerted its antioxidative effect regardless of whether it covered the oil or was dispersed in it.
We investigated the effect of the alkyl-chain length of anionic surfactants on the skin using an in vitro model. The evaluated anionic surfactants were sodium alkyl sulfate (AS) and sodium fatty acid methyl ester sulfonate (MES), which had different alkyl-chain lengths (C8–C14). Skin tissue damage and permeability were examined using a reconstructed human epidermal model, LabCyte EPI-MODEL24. Skin tissue damage was examined by measuring cytotoxicity with an MTT assay. Liquid chromatography/tandem mass spectrometry (LC/MS-MS) and liquid chromatography/mass spectrometry (LC/MS) were used to detect surfactants that permeated into the assay medium through an epidermal model. To assess the permeation mechanism and cell damage caused by the surfactants through the epidermis, we evaluated the structural changes of Bovine Serum Albumin (BSA), used as a simple model protein, and the fluidity of 1,2-dipalmitoyl-sn-glycero-3-phosphpcholine (DPPC) liposome, which serves as one of the most abundant phospholipid models of living cell membranes in the epidermis. The effects of the surfactants on the proteins were measured using Circular Dichroism (CD) spectroscopy, while the effects on membrane fluidity were investigated by electron spin resonance (ESR) spectroscopy. ET50 (the 50% median effective time) increased as follows: C10 < C12 < C8 < C14 in AS and C8, C10 < C12 < C14 in MES. The order of permeation through the LabCyte EPI-MODEL24 was C10 > C12 > C14, for both AS and MES. For both AS and MES, the order parameter, which is the criteria for the microscopic viscosity of lipid bilayers, increased as follows: C10 < C12 < C14, which means the membrane fluidity is C10 > C12 > C14. It was determined that the difference in skin tissue damage in the LabCyte EPI-MODEL24 with C10 to C14 AS and MES was caused by the difference in permeation and cell membrane fluidity through the lipid bilayer path in the epidermis.
Cellobiose lipids (CLs) are asymmetric bolaform biosurfactants, which are produced by Cryptococcus humicola JCM 10251 and have fungicidal activity. In this study, the sodium salts of CLs (CLNa) were prepared to improve aqueous solubility of the CLs, and their surface and gelation properties in aqueous solutions were examined by surface tension, rheology, and freeze-fracture transmission electron microscopy (FF-TEM) measurements. The surface tension measurements revealed that the CLNa have high surface activity: CMC1 and γCMC1 are 0.1 mg/mL and 34.7 mN/m, respectively. It was also found that the CLNa form giant micelles above their CMC, whose average size is 116.6 ± 31.9 nm. Unlike conventional surfactants, the surface tension reduced further with an increase in concentration and the aqueous solution became viscous at the minimum gelation concentration (MGC: 5.0 mg/mL). In rheological studies, the obtained gels proved to be rather soft and their sol-gel temperature was found to be approximately 50℃. FF-TEM observation of the gels showed 3D supramolecular structures with an entangled fibrous network. Since the present CLNa aqueous gels have a degree of fungicidal activity, they could be useful for novel multifunctional soft materials applicable to the food and cosmetic industries.
Feruloylated lipids are esters of ferulic acid, which have antioxidation and UV-absorbing activities. In this study, lipophilic feruloylated lipids were prepared by the enzymatic transesterification of ethyl ferulate (EF) with distearin. Effects of different diacylglycerols as feruloyl acceptors were compared. Effects of transesterification variables were studied and optimized using response surface methodology. Under the optimized conditions (reaction temperature 78°C, reaction time 24 h, and enzyme load 14%), EF conversion was 97.6±2.2%, and the lipophilic feruloylated lipids prepared by the transesterification were consisted of 43.2±0.9% feruloylated monoacylglycerols (FMAG) and 33.3±1.3% feruloylated diacylglycerols (FDAG), respectively. Analysis of variance (ANOVA) showed that the regression equation was adequate for predicting the transesterification. The activation energies for the transesterification of EF with distearin to form lipophilic FMAG + FDAG and the side reaction hydrolysis of EF to form glyceryl ferulate + glyceryl diferulate were 57.75 and 40.31 kJ/mol, respectively.
The aim of this research was to determine the chemical constituents and toxicities of the essential oil derived from Amomum tsaoko Crevost et Lemarie fruits against Tribolium castaneum (Herbst) and Lasioderma serricorne (Fabricius). Essential oil of A. tsaoko was obtained from hydrodistillation and was investigated by gas chromatography–mass spectrometry (GC-MS). GC-MS analysis of the essential oil resulted in the identification of 43 components, of which eucalyptol (23.87%), limonene (22.77%), 2-isopropyltoluene (6.66%) and undecane (5.74%) were the major components. With a further isolation, two active constituents were obtained from the essential oil and identified as eucalyptol and limonene. The essential oil and the two isolated compounds exhibited potential insecticidal activities against two storedproduct insects. Limonene showed pronounced contact toxicity against both insect species (LD50 = 14.97 μg/adult for T. castaneum; 13.66 μg/adult for L. serricorne) and was more toxic than eucalyptol (LD50 = 18.83 μg/adult for T. castaneum; 15.58 μg/adult for L. serricorne). The essential oil acting against the two species of insects showed LD50 values of 16.52 and 6.14 μg/adult, respectively. Eucalyptol also possessed strong fumigant toxicity against both insect species (LC50 = 5.47 mg/L air for T. castaneum; 5.18 mg/L air for L. serricorne) and was more toxic than limonene (LC50 = 6.21 mg/L air for T. castaneum; 14.07 mg/L air for L. serricorne), while the crude essential oil acting against the two species of insects showed LC50 values of 5.85 and 8.70 mg/L air, respectively. These results suggested that the essential oil of A. tsaoko and the two compounds may be used in grain storage to combat insect pests.
The magnetic Fe3O4/SBA-15 composites were prepared, and treated with 3-aminopropyltriethoxysilane as a carrier material for enzyme immobilization. The immobilization of Candida rugosa lipase onto the amino-functionalized Fe3O4/SBA-15 composite was investigated by using glutaraldehyde as a coupling reagent. The immobilized lipase was then employed as a biocatalyst for the interesterification of soybean oil and methyl stearate in a laboratory-scale operation at 45°C. Various techniques, such as Fourier transform infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), and vibrating sample magnetometry (VSM), were used for the characterization of the immobilized lipase composite. The immobilized lipase behaved superparamagnetic and showed excellent response at applied magnetic field. The obtained results showed that the immobilized lipase could efficiently catalyze the interesterification reaction. Moreover, the interesterification reaction parameters, such as reaction temperature, substrate ratio and reaction time were investigated regarding the stearoyl incorporation into the triacylglycerols. Further, the immobilized lipase proved to be easily separated from the reaction mixture by applying an external magnetic field and to be stable in the repeated use for four cycles.
The leaf essential oils of seven Vietnamese species of the genus Cinnamomum were analyzed by gas chromatography-flame ionization detector (GC-FID) and gas chromatography-mass spectrometry (GC/MS). The results showed that the species fall into three groups in which one group contains aromatic components, while the second group contains both terpenes and aromatic constituents and the third group contains only terpene constituents. The first group had only Cinnamomum curvifolium as its member and produced oil rich in benzyl cinnamate and benzyl benzoate. The second group producing mixture of phenylpropanoids and oxygenated monoterpene components includes leaves of Cinnamomum kunstleri (methyl eugenol, terpinen-4-ol and 1,8-cineole) and Cinnamomum mairei (eugenol, 1, 8-cineole, neryl acetate and eugenol acetate). The third group rich in terpene constituents could also be divided into two classes. The first class produced oils rich in monoterpene components and includes Cinnamomum damhaensis (linalool, α-pinene, β-pinene and 1,8-cineole), Cinnamomum cambodianum (linalool and terpinen-4-ol) and Cinnamomum caryophyllus (1,8-cineole, α-pinene and camphene). The second class contains oil with abundance of sesquiterpene compounds and peculiar to Cinnamomum rigidifolium (α-selinene, β-caryophyllene and α-copaene). This paper discusses further the chemotaxonomic importance of these results and previous data on essential oils of Cinnamomum species analysed from Vietnam.
Chloropropanol (CP) esters are a class of thermally-induced toxicants that are mainly formed in refined edible oils. The structural diversity of these esters presents significant analytical challenges which have often been overcome through analysis of their corresponding free alcohols after a hydrolysis step. Mass spectrometry-based methodologies incorporating characteristic fragmentation patterns of particular isomers of CP esters greatly facilitates their identification. The electron ionization mass spectra (EIMS) of various isomers of synthetic and commercially available 13C- and 2H-labeled CP ester standards of palmitic (C16) and other short chain fatty acids (C3 to C10) were generated and analyzed using GC/MS. Short chain CP esters were synthesized by reacting their respective acid anhydrides with the corresponding 3-chloro- and 2-chloro- propanediols in addition to 1,3-dichloro- and 1,2-dichloropropanols. Five fragmentation pathways were identified. Four of the five pathways, such as α-cleavage, McLafferty rearrangement, α-H rearrangement and cyclic acyloxonium ion formation, were characteristic of CP mono- and diesters. The remaining pathway generating chloronium ion was found only in dichlorinated isomers. The proposed fragmentation pathways for the palmitic acid esters were confirmed through the use of 13C- and 2H-labeled CP ester standards of palmitic acid, and the generality of identified fragmentation patterns was confirmed through the identification of equivalent ions in the mass spectra of short chain fatty acids (C3 to C16). Characteristic ions that were identified in this study retaining the chlorine atom in their structures can be considered as potential markers for the presence of CP esters.
The selective preparation of monobenzyl glyceryl ethers, which are potential commodity chemicals with special functions, was explored to find new applications for glycerol. Among the acid catalysts investigated (sulfuric acid, heteropoly acid, NafionR, and zeolite), Zeolite Socony Mobil–5 (ZSM-5) afforded better results. The reaction of equimolar amounts of glycerol and benzyl alcohol at 150ºC for 7 h in the presence of 2 wt% ZSM-5 selectively afforded 3-(benzyloxy)propane-1,2-diol with a very small amount of the corresponding 2-benzyloxy isomer in 86% gas chromatography yield.
Capsular polysaccharides (SPS) are the integral component of gram-negative bacteria, and also have potential uses as vaccines. In this paper, interaction of anionic SPS, isolated from Klebsiella K28, K43, K51 and K20, with cationic surfactants and cationic-nonionic mixed surfactants were investigated by turbidimetric titration, viscometric method. Variation of size and zeta-potential was measured using dynamic light scattering method. Due to binding of the surfactants size enhancement and charge reversal takes place. The interaction between oppositely charged polymer-surfactants are governed by the nature of the charged head group and of the counter ion, charge density and rigidity of the polymer architecture, CMC of the surfactant systems, concentration of surfactant (Cs). The binding is influenced both by electrostatic and hydrophobic interaction.
In this study, we successfully prepared titania/silica composite films modified with silane coupling agents having amino groups and investigated their bovine serum albumin (BSA) adsorption/desorption behavior under light irradiation. XRD patterns and ATR/FT-IR spectra of the films revealed the formation of titania/silica composite films modified with silane coupling agents. In these films, the adsorption and desorption of BSA could be controlled by light irradiation, through the locally photoinduced superhydrophilic titania surface.