Aroma Release from Solid Droplet Emulsions: Effect of Lipid Type

Aroma compounds partition between the different phases of a food emulsion and the headspace but only those in the headspace are perceived. Phase transitions in the lipid droplets profoundly affect the position of the partitioning equilibria and hence headspace aroma concentration. The release of four volatile aroma compounds (ethyl butanoate, pentanoate, heptanoate and octanoate) from eicosane, hydrogenated palm fat or Salatrim^® emulsions stabilized with sodium caseinate were investigated as a function of fat crystallization, particle size and droplet concentration. For all compounds, the headspace aroma concentration in equilibrium with solid droplet emulsions was significantly higher than that in equilibrium with liquid droplet emulsions. The partitioning of volatile aroma compounds from emulsion does not depend on the type of liquid lipid, however, the interactions between solid lipid droplets and aroma compounds are significantly influenced by the nature of the crystalline fat. Notably, partitioning into the headspace was much lower for solid triglyceride droplet emulsions than for solid alkane emulsions. It was proposed that both residual liquid lipid in solid triglycerides and aroma co-crystallization with solid lipid could be responsible for higher aroma absorption by solid triglycerides.     

Variation in Properties of Chitosan Prepared at Different Alkali Concentrations from Squid Pen and Shrimp Shell

Chitin from squid pen (Loligo sp.) and kiddi shrimp shell (Parapenaeopsis stylifera) were treated at room temperature (30 ± 2°C) with four different concentrations of sodium hydroxide: 20, 30, 40, and 50% w/w. With 50% sodium hydroxide solution, within 108 h, the chitin from squid pen was deacetylated to give chitosan. But it required 126 h at 40% and 144 h at 30% concentration of sodium hydroxide. In the case of chitin from Parapenaeopsis stylifera, complete deacetylation took place after 120 h and 168 h at 50 and 40% concentrations of sodium hydroxide, respectively. But shrimp shell on treatment with 20 and 30% sodium hydroxide solutions and squid pen kept at 20% sodium hydroxide were not sufficiently deacetylated even after 480 h. Properties like degree of deacetylation, viscosity and molecular weight of the prepared chitosan samples were studied. Minimum alkali concentration required for the formation of chitosan at room temperature was found to be 30% for squid chitin and 40% for shrimp chitin. With the increase in the time of deacetylation, decreases in molecular weight and viscosity were observed in chitosan from both sources. Maximum viscosity was recorded by chitosan prepared from squid pen using 30% sodium hydroxide solution at room temperature.     

Ionic liquid mediated nano-composite polymer gel electrolyte for rechargeable battery application

ABSTRACT

Nano-composite polymer gel electrolytes (NPGEs) based on polymer poly(vinylidene fluoride-co-hexafluoropropylene) PVdF-HFP, ionic liquid, 1-butyl-3- methylimidazolium bis(trifluoromethanesulfonyl)imide BMIMTFSI, Li-salt along with the addition of SiO₂ nanoparticles have been synthesized and characterized by various techniques. Prepared NPGEs show high room temperature ionic conductivity (~10^?3 S/cm) and have a wide electrochemical window (ECW) (~3.3–3.5 V). The galvanostatic charge/discharge profile was studied by sandwiching best performing NPGEs between a LiFePO₄ cathode and lithium metal anode. The specific discharge capacity of the cell (Li/NPGE/LiFePO₄) room temperature at 0.1C rate is found to be 138 mAh/g.     

Synthesis and Physico-Chemical Characterization of Halogenated Partly Aromatic Cardo Copolyesters

Copolyesters of 1,1′-bis(3-methyl-5-chloro-4-hydroxy phenyl) cyclohexane (0.0025 mol), ethylene glycol/propylene glycol/1, 4-butanediol/1,6-hexanediol (0.0025 mol) and terephthaloyl chloride (0.005 mol) have been synthesized by interfacial polycondensation technique by using water-chloroform (4:1 v/v) as an interphase, sodium hydroxide (0.125 mol) as an acid acceptor and cetyl trimethyl ammonium bromide (50 mg) as an emulsifier. The reaction time and temperature were 3 h and 0°C, respectively. The yield of copolymers was 85–87%. Copolyesters are soluble in common solvents and possess moderate molecular weights. The structures of copolyesters are supported by FT-IR and ¹HNMR spectral data. Copolyesters are characterized for their viscosity in chloroform and 1,2-dichloroethane at 30, 35 and 40°C, densities by floatation method (1.139–1.2775 g cm^?3). It is observed that both [η] and density of copolyesters decreased with increase in alkyl chain length. Copolyesters possess excellent hydrolytic stability against water and 10% each of acids, alkalis and salt at room temperature. The observed wt. % change is ±3.15% in the selected environments. A 30 μm thick C1MPT film has 17.8 MPa tensile strength, 50.1 kV mm^?1 electric strength and 2.2 × 10¹² ohm cm volume resistivity. Copolyesters possess high T_g (148–172°C) and are thermally stable up to about 411–426°C and followed single step degradation kinetics involving 70–75% weight loss with 20–24% residual weight above 650°C. Copolyesters followed 1.19–1.94 order degradation kinetics. Activation energy and frequency factors are increased with alkyl chain length.     

Inhibition of Mevalonate Pathway and Synthesis of the Storage Lipids in Human Liver-Derived and Non-liver Cell Lines by <Emphasis Type="Italic">Lippia alba</Emphasis> Essential Oils

The essential oils (EOs) of Lippia alba, an herb extensively used as a folk medicine in Latin America, are today promoted as an effective means of eliminating problems caused by hyperlipemia. We hypothesized that L.alba EOs inhibited cholesterol and triacylglycerols synthesis and decreased the intracellular depots of those lipids (lipid droplets), mechanisms involving the induction of a hypolipidemic response. Our aim was, therefore, to evaluate the hypolipogenic capability of the EOs of four L. alba chemotypes on liver-derived (HepG2) and non-liver (A549) human cell lines and to identify the potential biochemical targets of those chemotypes, particularly within the mevalonate pathway (MP). [¹⁴C]Acetate was used as radioactive precursor for assays. Lipid analyses were performed by thin-layer and capillary gas chromatography, lipid droplets analyzed by fluorescence microscopy, and HMGCR levels determined by Western blot. In both cell lines, all four chemotypes exerted hypocholesterogenic effects within a concentration range of 3.2–32 µg/mL. Nonsaponifiable lipids manifested a decrease in incorporation of [¹⁴C]acetate into squalene, lanosterol, lathosterol, and cholesterol, but not into ubiquinone, thus suggesting an inhibition of enzymes in the MP downstream from farnesyl pyrophosphate. The tagetenone chemotype, the most efficacious hypocholesterogenic L. alba EO, lowered HMGCR protein levels; inhibited triacylglycerols, cholesteryl esters, and phospholipids synthesis; and diminished lipid droplets in size and volume. These results revealed that L. alba EOs inhibited different lipogenic pathways and such lipid-lowering effects could prove essential to prevent cardiovascular diseases.     

The evidence of phase separation droplets in the crystallization process of a Li2O-Al2O3-SiO2 glass with TiO2 as nucleating agent – An X-ray diffraction and (S)TEM-study supported by EDX-analysis

Lithiumalumosilicate glasses are of great importance for industrial applications, because they enable the preparation of glass ceramics with coefficients of thermal expansion close to zero. While detailed studies of the effect of ZrO₂ on nucleation and crystal growth have already been performed in recent years, the effect of TiO₂ was up to now not reported in detail. It is shown for the first time, that liquid/liquid phase separation is the initial step of nucleation in lithiumalumosilicate glasses containing TiO₂. During temperature treatment above the glass transition temperature, at 740 °C for 0.25–24 h, in the formed droplets, TiO₂ nanocrystals precipitate. The formed phases were investigated by XRD- and TEM and STEM-EDX to illustrate the phase developments as well as the resulting microstructures and the local enrichments of the respective components as a function of time.Longer crystallization times resulted in the formation of crystalline lithiumalumosilicate (LAS) with a high-quartz structure. These crystals are notably larger than the TiO₂ crystals and are growing with increasing treatment time and temperature. The evidence of anatase formation was obtained from high resolution TEM from the lattice spacings because it cannot be distinguished from the high quartz structure using XRD.     

Improvement of the photovoltaic properties for P3HT:PCBM system annealed at the temperature in liquid crystalline regions induced by liquid crystal molecules

The poly(3-hexylthiophene):[6, 6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) bulk heterojunction organic photovoltaics (BHJ OPVs) showed a maximum value of 3.5 % by incorporating of 6 wt% nematic liquid crystals (NLCs) of 4-octyloxy-4′-cyanobiphenyls (8OCB) after annealing at the temperature of 70 °C in liquid crystalline transitions. The 8OCB was immiscible with P3HT, and the melting temperature of P3HT was not influenced at 8OCB doping amount below 10 wt%. Based on the UV–vis analysis, the conjugation length and chain order of P3HT should be the highest at 8OCB content of 6 wt% after annealing at 70 °C. The reflection peak of P3HT shifted to lower positions as the annealing temperature increasing from 70 to 130 °C, indicating that PCBM and 8OCB molecules could be incorporated into the lamellar spacing of P3HT crystallites at high annealing temperatures. The improvement of the solar cell device after annealing at 70 °C is probably due to the optimized phase separation morphology and relatively higher hole mobility in P3HT:PCBM:8OCB system. The 8OCB molecules in the liquid crystalline state are supposed to be a good template for the crystallization of P3HT, as well as the phase separation between P3HT and PCBM.     

Impact of Phosphoethanolamine Reverse Micelles on Lipid Oxidation in Bulk Oils

Phospholipids are important minor components in edible oil that play a role in lipid oxidation. Surface active phospholipids have an intermediate hydrophilic–lipophilic balance value, which allows them to form association colloids such as reverse micelles in bulk oil. These association colloids can influence lipid oxidation since they create lipid–water interfaces where prooxidants and antioxidants can interact with triacylglycerols. In this study, we examined the formation of reverse micelles in a stripped oil system by dioleoyl phosphoethanolamine (DOPE) and the effect of these physical structures on lipid oxidation kinetics. The critical micelle concentration (CMC) of DOPE was approximately 200 µmol/kg oil at 45 °C. Oxidation kinetics studies showed that DOPE was prooxidative when it was above its CMC (400 and 1,000 µM), reducing the lag phase from 14 days (control) to 8 days. The addition of combinations of DOPE and dioleoyl phosphocholine (DOPC) resulted in formation of mixed micelles with a CMC of 80 µmol/kg oil at 45 °C. These mixed micelles were also prooxidative when concentrations (100 and 500 µM) were above the CMC, decreasing the lag phase from 14 to 8 days. These findings provide a better understanding of the role of phospholipids in lipid oxidation of edible oil and could contribute to better antioxidant solutions.     

Amaranth Oil Increased Fecal Excretion of Bile Acid but Had No Effect in Reducing Plasma Cholesterol in Hamsters

Hamsters were fed for 4 weeks on four different diets: control (C) (balanced diet containing 20 % corn oil as the lipid source), hypercholesterolemic (H) (identical to C but containing 12 % coconut oil, 8 % corn oil and 0.1 % cholesterol as the lipid source), amaranth oil (A) (identical to H without corn oil but with amaranth oil), and squalene (S) (identical to H but admixed with squalene in the ratio found in amaranth oil). There were no significant differences in lipid profile, and in the cholesterol excreted in the animals’ feces from amaranth oil (A) and squalene (S) groups. Fecal excretion of bile acids was greater in the amaranth oil (A) and squalene groups (S) as compared to the other groups. The scores of steatosis and parenchymal inflammation observed in the amaranth oil (A) and squalene groups (S) were superior to the ones observed in the other groups. Our findings demonstrated that amaranth oil, and its component squalene, increased the excretion of bile acids but did not have a hypocholesterolemic effect in hamsters fed on a diet containing high amounts of saturated fat and cholesterol.     

Fat Crystals Influence Methylcellulose Stabilization of Lipid Emulsions

Oil-in-water emulsions stabilized with methylcellulose (MC) varied in stability depending on the composition of the fat phase. When droplets were composed entirely of liquid oil, MC was able to form a continuous, protective film around the droplets. Therefore, when two liquid oil droplets were brought into contact, they underwent extreme shape deformation but did not coalesce, even when excess force was used. Subsequently, interfacial crystals extending into the aqueous phase from palm kernel oil droplets were aimed into an entirely liquid oil droplet. The MC-coated droplet would deform wherever the crystal contacted; however, the protruding crystals could not penetrate into the liquid oil droplet. Conversely, when the target droplet was composed of a small amount of solid fat that resulted in localized crystalline regions and the interfacial crystals of the second droplet were aimed at this region, they then easily pierced the droplet. This demonstrates that MC is an excellent stabilizer for liquid oil droplets but internal lipid crystals within fat globules can alter MC surface conformation to allow for crystal penetration and arrested coalescence.     

Degradation of Epoxy-Steel Single Lap Joints Immersed in Water

Exposure to environmental factors, especially moisture, is recognized as the major cause of degradation of adhesive joints. In this work, complementing a previous study on exposure to moisture, single lap joints were subjected to immersion in water, up to five weeks, at room temperature and 50 °C. The material of the adherends was mild steel, and the adhesive was a bi-component epoxy. The specimens were fabricated using the open-face technique. Mechanical testing at the end of the relevant period of immersion showed an initial loss of ultimate load, after one week at 50 °C or two at room temperature; then, the strength remained practically constant over the remaining time. The loss was more accentuated after immersion at 50 °C, about 70%, than at room temperature, about 30%. Also a reduction in stiffness of the joints was measured, again dramatic (about 70%) after immersion at 50 °C, moderate (about 10%) after room temperature immersion. Optical examination, performed before closing the open-face specimens and after mechanical testing, showed that the major damage mechanism was the formation of blisters filled by liquid at the primary adherend/primary adhesive interface, causing the failure mode to change from cohesive to interfacial.     

Development of a new procedure for lipid extraction from Hevea brasiliensis natural rubber

Non‐isoprene components and especially lipids have been reported to be involved in some key properties of natural rubber. Unfortunately, these results are hardly comparable due to different extraction methods. This work aimed to optimize lipid extraction from natural rubber either in the liquid state (latex) or in the dry state (unsmoked sheets). Extraction of unsmoked sheets from the RRIM 600 clone was carried out with different combinations of organic solvents (chloroform/methanol and hexane/isopropanol mixes). Chloroform/methanol (2 : 1 vol/vol) was found to be the most suitable for lipid extraction from unsmoked sheet rubber. The lipid extraction yield was improved by increasing the exchange surfaces by grinding rubber under liquid nitrogen and extracting the ground rubber for 6 h at room temperature, leading to 1.82% lipid extraction yield (versus dry rubber). Concerning latex extraction, the problem of lipid entrapment in the coagulum from immediate coagulation of latex in the solvent was solved by preliminary two times dilution of latex, giving a 3.24% extract (versus dry rubber) containing a minimum quantity of contaminating polyisoprene. Concerning the nature of lipids, dilution increased mainly neutral lipid extraction, which may suggest that neutral lipids were those entrapped by coagulation.     

In-Situ X-Ray Studies of Cocoa Butter Droplets Undergoing Simulated Spray Freezing

Spray freezing offers a novel manufacturing route to fine powders with controlled crystalline structures. Here we simulate this process by freezing (using a cold dry air flow) suspended 2-mm diameter droplets of cocoa butter such that X-ray diffraction observation of the droplet’s evolving crystalline structure is possible in situ. Initially the Form I polymorph is observed in the droplets: this transforms to Form II over a few minutes and then to Form III over a few hours, even at 0 °C. If the droplet is then warmed to 24 °C, further transformation to Form IV and then Form V occur over approximately 2 h. These phase transformations are similar to those which would be expected in a bulk cocoa butter sample, but occur significantly faster in the droplets. Small crystal sizes in the frozen droplet, resulting from the droplet’s low Biot number (and thus even temperature distribution), is postulated as being the cause for the unexpectedly rapid evolution in the crystal habit.     

Supported Gold Nanoparticles Catalysts for Solvent-free Selective Oxidation of Benzylic Compounds into Ketones at 1 atm O2

Supported gold nanoparticles catalyst (Au/TiO₂) was investigated for the oxidation of benzylic compounds into corresponding ketones without any organic solvent at 1 atm O₂ under mild reaction conditions (≤100 °C). For instance, indan was oxidized with conversion of 46% and 1-indanone selectivity of 90% at 90 °C for 24 h. Effect of various reaction parameters viz., temperature, time, and effect of a range of supports was studied for the oxidation of indan. The conversion of indan and selectivity of 1-indanone over recycled catalyst remains almost same.     

Effect of microencapsulation and spray drying on oxidative stability of flaxseed oil and its release behavior under simulated gastrointestinal conditions

Flaxseed oil is one of the richest sources of omega-3 fatty acid (α-linolenic acid, ALA). It contains high amounts of polyunsaturated fatty acids, making it extremely susceptible to oxidation. In the present study, flaxseed oil was stabilized using microencapsulation followed by spray drying and studied for its oxidative stability in terms of peroxide value (PV), thiobarbituric acid, and p-anisidine value at room temperature (35 ± 1°C) and low temperature (4–7°C) storage for 6 months. Results revealed that the developed flaxseed oil powder was stable throughout the storage period and PV remained below to the maximum permissible limit (≤5 mEq/kg oil) prescribed by the Codex Alimentarius Commission. The fatty acids profile measured by gas–liquid chromatography indicated a 14.28–15.13% decrease in ALA content in flaxseed oil as a result of microencapsulation and storage at room temperature. In vitro digestion behavior of microcapsules showed 4.39 ± 0.53 to 19.87 ± 0.47% release of flaxseed oil under simulated gastric continued, whereas under gastrointestinal conditions it was 20.00 ± 3.66 to 59.99 ± 9.29%.     

An Improved Method for Determining Medium- and Long-Chain FAMEs Using Gas Chromatography

The existing protocols for analyzing fatty acid methyl esters (FAMEs) using a one-step acetyl chloride (AC) catalyzed transesterification and extraction procedure cannot accurately determine the medium- and long-chain fatty acids simultaneously in clinical (enteral, parenteral) formulations. For example: (1) addition of AC at room temperature generates an exothermic reaction that often results in loss of sample and possible injury to the analyst; (2) certain polyunsaturated fatty acids (PUFAs) are less stable at elevated temperatures during the transesterification and contribute to the over-estimation of the C16:0 and C18:1 fatty acids; and (3) the flame-ionization detector (FID) response varies depending on the carbon chain length of the fatty acids, that consequently impacts the underestimation of medium-chain fatty acid (C6–C10) recoveries. To overcome these deficiencies and accurately determine FAMEs, we have developed an improved one-step transesterification method that employs the addition of AC in tubes kept on a dry ice bath, the transesterification at room temperature, and the data analysis using relative response factors. Using this modified protocol, we determined the fatty acid composition of lipid emulsions (Omegaven^® and Lipidem^®) on a Shimadzu GC2010 gas chromatography (GC) system using a capillary GC column (Zebron ZB-WAX plus, 30 m, 0.25 mm ID, 0.25 μm). Our data suggest that the improved method can be easily used to accurately determine fatty acids (C6–C24) in functional foods and lipid emulsions.     

Synthesis,characterization, swelling-deswelling properties of Novel nanoparticle-hydrogel containing core chitosan and their cyclohexanone-crosslinked counterparts

Novel Chitosan-cyclohexanone Mannich based hydrogel nanoparticles (CCMb1-4) were prepare via the reaction of chitosan with different concentration of 2, 6-bis (piperidin-1-ylmethyl) cyclohexanone. 2HCl (1%, 5%, 10% and 15% wt/wt) at 70–80°C for 7 h. These hydrogels were subjected to equilibrium swelling studies at room temperature in solutions of pH 2, 4, 6 and 8. The (CCMb1-4) showed maximum percent swellability at pH = 2.0. Furthermore, the swelling of the (CCMb1-4) followed Fickian diffusion. This preliminary investigation of chitosan-based interpolymeric hydrogels showed that they may be exploited to expand the utilization of these systems in drug delivery applications.     

Acidolysis Reaction of Terebinth Fruit Oil with Palmitic and Caprylic Acids to Produce Low Caloric Spreadable Structured Lipid

The lipase (Lipozyme IM from Rhizomucor miehei) catalyzed acidolysis reaction of terebinth (Pistacia terebinthus L.) fruit oil with caprylic and palmitic acid in hexane was investigated in a batch system. The effect of reaction conditions and relationship among them were analyzed and optimized by response surface methodology with a four-factor five-level central composite rotatable experimental design. The four major factors chosen were enzyme load (10–20 wt%), reaction time (12–20 h), reaction temperature (45–60 °C) and substrate mol ratio (TO:PA:CA, 1:2.3–4.1:1.15–2.05). Optimum reaction conditions for reaction time, temperature, enzyme load and substrate mole ratio were 12 h, 45 °C, 10 wt% and 1:4.1:2.05, respectively. The maximum yield of desired triacylglycerols (TAG) obtained at these optimum conditions was 50.87 %. Produced structured lipid had a caloric value which was 1.5 % lower than that of terebinth fruit oil. Its solid fat content was found comparable with commercially available margarines. The relative activity of lipase was well maintained in up to 10 repeated cycles.     

Matrix physical structure effect on the electro-optic characteristics of thiol-ene based H-PDLC films

The physical and mechanical properties of several thiol-ene based polymers and their mixtures with the liquid crystal, E7, were characterized to probe their relationship with the liquid crystal film electro-optic performance properties. Kinetic data suggests that high conversion is achieved for each thiol-ene combination. Pre-polymerization phase diagrams indicate that each thiol-ene/E7 mixture phase separates well below room temperature, and thus prior to polymerization at room temperature all are in a single phase. Holographic polymer dispersed liquid crystals (HPDLC) were fabricated for several thiol-ene and E7 mixtures, and electro-optical parameters characterized to probe the relationship between the thiol-ene network properties and the electro-optic performance of the HPDLCs. The photocured matrices exhibited glass transitions and tan δ peak maxima that ranged from temperatures below 0 °C to well above room temperature. There is a clear correlation between the physical nature of the matrix and the electro-optic switching parameters with H-PDLC films fabricated from trithiol-pentaerythritol triallylether, all of which exhibit glass transition temperatures below 0 °C, having the fastest switching times and lowest switching voltages at room temperature. Also, in each case higher liquid crystalline concentration resulted in lower switching voltages.     

Size Controlling of L1<Subscript>0</Subscript>-FePt Nanoparticles During High Temperature Annealing on the Surface of Carbon Nanotubes

Mono-size FePt nanoparticles with particles size about 2.5 nm have been prepared by polyol method on the surface of carbon nanotubes (CNTs). The CNTs functinalization time and the mass ratio of nanoparticles to CNTs affects on the CNTs surface coating. The as-synthesis nanocomposites have a superparamagnetic behavior with chemically disordered fcc structure at room temperature and they can be transformed into chemically ordered fct structure after thermal annealing above 600 °C. Their magnetic behavior changes from the superparamagnetic to the ferromagnetic with a large coercivity up to 0.83 T for the nanocomposites which annealed at 800 °C. The CNTs surfaces as a substrate prevent the agglomeration of nanoparticles during high temperature annealing and the FePt nanoparticles after annealing at 800 °C have finite size with an average about 10 nm. The structure, composition and magnetic properties of nanocomposite were characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and vibrating sample magnetometer.