Fat content and macroscopic properties of fat network formulation result in final products in chocolate industry. The knowledge of physical properties is required in regard to stability of final food products resulting to quality. The study was carried out to investigate the thermal behavior, solid fat content and hardness of Rambutan fat (RF), cocoa butter and mixtures between two fats. The results found that the mixtures can be compatibility; the cocoa butter indicated the higher of solid fat content at room temperature more than RF and other mixtures. The RF had the highest melting point in both non-stabilized and stabilized form among cocoa butter and their mixtures. The hardness behavior showed lower in the mixture 1 and RF. For the phase behavior of crystallization exhibited the similar for all samples whereas the time of crystallization and temperatures were different. Therefore, the RF might be possible source of cocoa butter substitute with suitable proportion in the manufacturing chocolate and confectionery products.
In the presence of guest 2,4'-bpy molecules or under acidic conditions, three compounds, [Cd(4,4'-bpy)(2)(H(2)O)(2)](ClO(4))(2).(2,4'-bpy)(2).H(2)O (1), [Zn(4,4'-bpy)(2)(H(2)O)(2)](ClO(4))(2).(2,4'-bpy)(2).H(2)O (2), and [Cu(4,4'-bpy)(2)(H(2)O)(2)](ClO(4))(4).(4,4'-H(2)bpy) (3), were obtained from the reactions of the metal salts and 4,4'-bpy in an EtOH-H(2)O mixture. 1 has a 2-D square-grid network structure, crystallizing in the monoclinic space group P2/n, with a = 13.231(3) Å, b = 11.669(2) Å, c = 15.019(3) Å, beta = 112.82(3) degrees, Z = 2; 2 is isomorphous with 1, crystallizing in the monoclinic space group P2/n, with a = 13.150(3) Å, b = 11.368(2) Å, c = 14.745(3) Å, beta = 110.60(3) degrees, Z = 2. The square grids superpose on each other into a channel structure, in which each layer consists of two pairs of shared edges, perfectly square-planar with an M(II) ion and a 4,4'-bpy at each corner and side, respectively. The square cavity has dimensions of 11.669(2) x 11.788(2) and 11.368(2) x 11.488(2) Å for 1 and 2, respectively. Every two guest 2,4'-bpy molecules are clathrated in each hydrophobic host cavity and are further stabilized by pi-pi stacking and hydrogen bonding interactions. The NMR spectra clearly confirm that both 1 and 2 contain 4,4'-bpy and 2,4'-bpy molecules in a 1:1 ratio, which have stacking interaction with each other in the solution. 3 crystallizes in the orthorhombic space group Ibam, with a = 11.1283(5) Å, b = 15.5927(8) Å, c = 22.3178(11) Å, Z = 4. 3 is made up of two-dimensional square [Cu(4)(4,4'-bpy)(4)] grids, where the square cavity has dimensions of 11.13 x 11.16 Å. Each [4,4'-H(2)bpy](2+) cation is clathrated in a square cavity and stacks with one pair of opposite edges of the host square cavity in an offset fashion with the face-to-face distance of ca. 3.95 Å. Within each cavity, the [4,4'-H(2)bpy](2+) cation forms twin three-center hydrogen bonds with two pairs of ClO(4)(-) anions. The results suggest that the guest 2,4'-bpy molecules and protonated [4,4'-H(2)bpy](2+) cations present in the reaction systems serve as structure-directing templates in the formation of the crystal structures and exclude self-inclusion of the networks having larger square cavities.
Cs2Pb(MoO4)2crystals were prepared by crystallization from their own melt, and the crystal structure has been studied in detail. At 296 K, the molybdate crystallizes in the low-temperature α-form and has a monoclinic palmierite-related superstructure (space group C2/m, a = 2.13755(13) nm, b = 1.23123(8) nm, c = 1.68024(10) nm, β = 115.037(2)°, Z = 16) possessing the largest unit cell volume, 4.0066(4) nm3, among lead-containing palmierites. The compound undergoes a distortive phase transition at 635 K and incongruently melts at 943 K. The electronic structure of α-Cs2Pb(MoO4)2was explored by using X-ray emission spectroscopy (XES) and X-ray photoelectron spectroscopy methods. For α-Cs2Pb(MoO4)2, the photoelectron core-level and valence-band spectra and the XES band representing the energy distribution of Mo 4d and O 2p states were recorded. Our results allow one to conclude that the Mo 4d and O 2p states contribute mainly to the central part and at the top of the valence band, respectively, with also significant contributions throughout the whole valence-band region of the molybdate under consideration.
This paper presents the effects of calcination time and sintering temperature on the properties of CaCu(3)Ti(4)O(12). Electroceramic material of CaCu(3)Ti(4)O(12) was prepared using a modified mechanical alloying technique that covers several processes, which are preparation of raw material, mixing and ball milling for 5 hours, calcination, pellet forming and, sintering. The objective of this modified technique is to enable the calcination and sintering processes to be carried out at a shorter time and lower temperature. The x-ray diffraction (XRD) analysis result shows that a single-phase of CaCu(3)Ti(4)O(12) was completely formed by calcination at 750 degrees C for 12 hours. Meanwhile, the grain size of a sample sintered at 1050 degrees C for 24 hours is extremely large, in the range of 20-50 mum obtained from field emission scanning electron microscopy (FESEM) images. The dielectric constant value of 14,635 was obtained at 10 kHz by impedance (LCR) meter in the sintered sample at 1050 degrees C. However, the dielectric constant value of samples sintered at 900 and 950 degrees C is quite low, in the range of 52-119.
Nanostructured lipid carriers (NLC) composed of solid and liquid lipids, and surfactants are potentially good colloidal drug carriers. Before NLC can be used as drug carriers, the cytotoxicity of their components must be ascertained. The cytotoxicity of solid lipids (trilaurin, palmitin, docosanoid acid, and hydrogenated palm oil [HPO]) and surfactants (Polysorbate 20, 80, and 85) were determined on BALB/c 3T3 cells. The HPO and Polysorbate 80 were least cytotoxic and used with olive oil in the formulation of NLC. The particle size, polydispersity index, zeta potential, specific surface area, and crystallinity index of the NLC were 61.14 nm, 0.461, -25.4 mV, and 49.07 m(2) and 27.12% respectively, while the melting point was 4.3 °C lower than of HPO. Unlike in serum-free, NLC incubated in fetal bovine serum-supplemented medium did not show particle growth, suggesting that serum proteins in medium inhibit nanoparticles aggregation. The study also showed that NLC was less toxic to BALB/c 3T3 cells than Polysorbate 80. Thus, NLC with olive oil, HPO, and Polysorbate 80 as components are potentially good drug carriers with minimal cytotoxicity on normal cells.
The formation of struvite crystals or magnesium ammonium phosphate (MgNH4PO4) in palm oil mill effluent (POME) occurs as early as in the secondary stage of POME treatment system. Its growth continues in the subsequent tertiary treatment which reduces piping diameter, thus affecting POME treatment efficiency. Hypothesis. The beneficial use of the crystal is the motivation. This occurrence is rarely reported in scientific articles despite being a common problem faced by palm oil millers. The aim of this study is to characterize struvite crystals found in an anaerobic digester of a POME treatment facility in terms of their physical and chemical aspects. The compositions, morphology and properties of these crystals were determined via energy dispersive spectroscopy (EDS), elemental analysis, scanning electron microscopy (SEM) and x-ray diffraction (XRD). Solubility tests were carried out to establish solubility curve for struvite from POME. Finally, crystal growth experiment was done applying reaction crystallization method to demonstrate struvite precipitation from POME. Results showed that high phosphorous (P) (24.85 wt%) and magnesium (Mg) (21.33 wt%) content was found in the struvite sample. Elemental analysis detected carbon (C), hydrogen (H), nitrogen (N) and sulfur (S) below 4 wt%. The crystals analysed by XRD in this study were confirmed as struvite with 94.8% struvite mineral detected from its total volume. Having an orthorhombic crystal system, struvite crystals from POME recorded an average density of 1.701 g cm-3. Solubility curve of struvite from POME was established with maximum solubility of 275.6 mg L-1 at pH 3 and temperature 40 °C. Minimum solubility of 123.6 mg L-1 was recorded at pH 7 and temperature 25 °C. Crystal growth experiment utilizing POME as the source medium managed to achieve 67% reduction in phosphorous content. This study concluded that there is a potential of harnessing valuable nutrients from POME in the form of struvite. Struvite precipitation technology can be adapted in the management of POME in order to achieve maximum utilization of the nutrients that are still abundant in POME. At the same time maximization of nutrient extractions from POME will also reduce pollutants loading in the final discharge.
Interesterification reaction involves rearrangement of the fatty acid radicals on the glycerol backbone, either randomly (chemical interesterification) or regioselectivity (enzymatic interesterification). Refined, bleached and deodourised palm oil (RBDPO) and palm kernel oil (RBDPKO) were blended in ratios from 25:75 to 75:25 (wt/wt). All blends were subjected to enzymatic (EI) and chemical interesterification (CI) using Lipozyme TL IM (4% w/w) and sodium methoxide (0.2% m/m) as the catalysts, respectively. The effect of EI and CI on the triacylglycerol (TAG) composition, thermal behaviour, polymorphism, crystal morphology and crystallisation kinetics were studied. The aim of this research is to characterise the nature of crystals in food product for certain desired structure. The crystallisation behaviour discussed in this study involves microstructure (PLM), polymorphism (XRD), thermal properties and crystallisation kinetics by DSC. The alteration in TAG composition was greater after CI as compared to EI with the reduction of LaLaLa (from 11.00% to 5.15%) and POO (from 14.28% to 4.87%). The DSC complete melting and crystallisation temperature of blend with 75% PO increased after CI, from 39.58 °C to 41.67 °C and from -30.84 °C to -28.33 °C, respectively. EI contributed to finer crystals than CI. However, the β' and β polymorph mixture and crystallisation kinetics (n = 2) of PO-PKO blends did not change after CI and EI. The knowledge on controlling crystallisation of RBDPO and RBDPKO blends is vital for proper processing condition like margarine production.
The stearin fraction of palm-based diacylglycerol (PDAGS) was produced from dry fractionation of palm-based diacylglycerol (PDAG). Bakery shortening blends were produced by mixing PDAGS with either palm mid fraction, PMF (PDAGS/PMF), palm olein, POL(PDAGS/POL) or sunflower oil, SFO (PDAGS/SFO) at PDAGS molar fraction of XPDAGS=0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%. The physicochemical results obtained indicated that C16:0 and C18:1 were the dominant fatty acids for PDAGS/PMF and PDAGS/POL, while C18:1 and C18:2 were dominant in the PDAGS/SFO mixtures. SMP and SFC of the PDAGS were reduced with the addition of PMF, POL and SFO. Binary mixtures of PDAGS/PMF had better structural compatibility and full miscibility with each other. PDAGS/PMF and PDAGS/SFO crystallised in β'+β polymorphs in the presence of 0.4-0.5% PDAGS while PDAGS/POL resulted in β polymorphs crystal. The results gave indication that PDAGS: PMF at 50%:50% and 60%:40% (w/w) were the most suitable fat blend to be used as bakery shortening.
The main goal of the present work was to assess the mechanism of crystallisation, more precisely the dominant component responsible for primary crystal formations and fat agglomerations. Therefore, DSC results exhibited significant effect on temperature transition; peak sharpness and enthalpy at palm stearin (PS) levels more than 40wt.%. HPLC data demonstrated slight reduction in the content of POO/OPO at PS levels less than 40wt.%, while the excessive addition of PS more than 40wt.% increased significantly PPO/POP content. The pNMR results showed significant drop in SFC for blends containing PS less than 40wt.%, resulting in low SFC less than 15% at body temperature (37°C). Moreover, the values of viscosity (η) and shear stress (τ) at PS levels over 40wt.% expressed excellent internal friction of the admixtures. All the data reported indicate that PPO/POP was the major component of primary nucleus developed. In part, the levels of PS should be less than 40wt.%, if these blends are designed to be used for margarine production.
Rambutan seed is usually discarded during fruit processing. However, the seed contains a considerable amount of crude fat. Hence, the objective of this study was to investigate the fat properties and antinutrient content of the seed during fermentation of rambutan fruit. Results showed that the crude fat content of the seed reduced by 22% while its free fatty acid content increased by 4.3 folds after 10 days of fermentation. Arachidic acid was selectively reduced and was replaced by linoleic acid from the seventh day of fermentation onwards. Only 14.5% of triacylglycerol remained in the seed fat at the end of fermentation. The complete melting temperature, crystallization onset temperature and solid fat index at 37 °C of the fermented seed fat were higher than that of non-fermented seed fat. The saponin and tannin contents of the seed were reduced by 67% and 47%, respectively, after fermentation.
The influence of diacylglycerol (DAG) combined with polyglycerol polyricinoleate (PGPR) on the stability of water-in-oil (W/O) emulsions containing hydrogenated palm oil (HPO) was studied. Polarized light microscope revealed that DAG promoted HPO to crystallize at the water-oil interface, providing the combination of Pickering and network stabilization effects. It was proposed that the molecular compatibility of fatty acids in DAG with HPO accounted for the promotional effect. The interfacial crystallization of DAG together with the surface activity of PGPR led to the formation of emulsions with uniform small droplets and high freeze-thaw stability. Further exploration of physical properties indicated that the combination of DAG and PGPR dramatically improved the emulsion's viscoelasticity and obtained a larger deformation yield. Water droplets in DAG-based emulsions acted as active fillers to improve the network rigidity. Therefore, DAG is a promising material to be used as emulsifier to enhance the physical stability of W/O emulsions.
High internal phase emulsions (HIPEs) show promising application in food and cosmetic industries. In this work, diacylglycerol (DAG) was applied to fabricate water-in-oil (W/O) HIPEs. DAG-based emulsion can hold 60% water and the emulsion rigidity increased with water content, indicating the water droplets acted as "active fillers". Stable HIPE with 80% water fraction was formed through the combination of 6 wt% DAG with 1 wt% polyglycerol polyricinoleate (PGPR). The addition of 1 w% kappa (κ)-carrageenan and 0.5 M NaCl greatly reduced the droplet size and enhanced emulsion rigidity, and the interfacial tension of the internal phase was reduced. Benefiting from the Pickering crystals-stabilized interface by DAG as revealed by the microscopy and enhanced elastic modulus of emulsions with the gelation agents, the HIPEs demonstrated good retaining ability for anthocyanin and β-carotene. This study provides insights for the development of W/O HIPEs to fabricate low-calories margarines, spread or cosmetic creams.
Diacylglycerols (DAG) of varying chain lengths were synthesized and the acyl migrated samples with different 1,3-DAG/1,2-DAG ratios were obtained. The crystallization profile and surface adsorption differed depending on DAG structure. C12 and C14 DAGs formed small platelet- and needle-like crystals at the oil-air interface which can better reduce surface tension and pack in an ordered lamellar structure in oil. The acyl migrated DAGs with higher ratios of 1,2-DAG showed reduced crystal size and lower oil-air interfacial activity. C14 and C12 DAG oleogels exhibited higher elasticity and whipping ability with crystal shells surrounding bubbles, whereas C16 and C18 DAG oleogels had low elasticity and limited whipping ability due to the formation of aggregated needle-like crystals and loose gel network. Thus, acyl chain length dramatically influences the gelation and foaming behaviors of DAGs whereas the isomers exert little influence. This study provides basis for applying DAG of different structures in food products.
This study aims to evaluate the effect of sucrose replacer mixtures (erythritol, mannitol, or tagatose in combination with inulin or polydextrose) on the crystal morphology, particle size distribution, rheology, melting properties, and fat polymorphism of dark compound chocolate. The result showed that the replacer mixture's hygroscopicity, particle size, and sugar crystal shape might significantly impact dark compound chocolate's rheological and textural properties but had no substantial impact on the melting properties and fat crystallization. Mannitol-containing samples exhibited the highest rheological value, likely related to their high moisture content, small particle size, and elongated crystal shape. Due to the similar specific surface area and comparable D90 value, the sample containing erythritol-polydextrose mixture resulted in a similar (P ≥ 0.05) Casson yield value (46.184 ± 2.45 Pa) compared to the sample containing sucrose (38.348 ± 1.68 Pa). It could be a potential sucrose replacer in the dark compound chocolate.
In this study, the effect of lecithin (LEC) on the crystallization and gelation of fruit wax (FW) with sunflower oil was researched. A synergistic effect on the gel strength was observed at FW : LEC ratios of 75 : 25 and 50 : 50, compared to the corresponding single component formulations (100 : 0 and 0 : 100). Even below the critical gelling concentration (Cg) of FW, the addition of lecithin enabled gel formation. Lecithin affected the thermal behavior of the structure by delaying both crystallization and gel formation. The phospholipid acted as a crystal habit modifier changing the microstructure of the oleogel, as was observed by polarized light microscopy. Cryo-scanning electron microscopy revealed a similar platelet-like arrangement for both FW as a single oleogelator and FW in combination with LEC. However, a denser structure could be observed in the FW : LEC oleogelator mixture. Both the oil-binding capacity and the thixotropic recovery were enhanced upon lecithin addition. These improvements were attributed to the hydrogen bonding between FW and LEC, as suggested by Raman spectroscopy. We hypothesized that lecithin alters the molecular assembly properties of the FW due to the interactions between the polar moieties of the oleogelators, which consequently impacts the hydrophobic tail (re)arrangement in gelator-gelator and solvent-gelator interactions. The lipid crystal engineering approach followed here offered prospects of obtaining harder self-standing structures at a lower oleogelator concentration. These synergistic interactions provide an opportunity to reduce the wax concentration and, as such, the waxy mouthfeel without compromising the oleogel properties.
BACKGROUND: Drug crystallization following application of transdermal and topical formulations may potentially compromise the delivery of drugs to the skin. This phenomenon was found to be limited to the superficial layers of the stratum corneum (~7 µm) in our recent reports and tape stripping of the skin samples was necessary. It remains a significant challenge to profile drug crystallization in situ without damaging the skin samples.
METHODS: This work reports the application of an X-ray microbeam via synchrotron SAXS/WAXS analysis to monitor drug crystallization in the skin, especially in the deeper skin layers. Confocal Raman spectroscopy (CRS) was employed to examine drug distribution in the skin to complement the detection of drug crystallization using SAXS/WAXS analysis.
RESULTS: Following application of saturated drug solutions (ibuprofen, diclofenac acid, and salts), CRS depth profiles confirmed that the drugs generally were delivered to a depth of ~15 - 20 µm in the skin. This was compared with the WAXS profiles that measured drug crystal diffraction at a depth of up to ~25 µm of the skin.
CONCLUSION: This study demonstrates the potential of synchrotron SAXS/WAXS analysis for profiling of drug crystallization in situ in the deeper skin layers without pre-treatment for the skin samples. [Figure: see text].
Drug permeation through the intercellular lipids, which pack around and between corneocytes, may be enhanced by increasing the thermodynamic activity of the active in a formulation. However, this may also result in unwanted drug crystallisation on and in the skin. In this work, we explore the combination of ATR-FTIR spectroscopy and multivariate data analysis to study drug crystallisation in the skin. Ex vivo permeation studies of saturated solutions of diclofenac sodium (DF Na) in two vehicles, propylene glycol (PG) and dimethyl sulphoxide (DMSO), were carried out in porcine ear skin. Tape stripping and ATR-FTIR spectroscopy were conducted simultaneously to collect spectral data as a function of skin depth. Multivariate data analysis was applied to visualise and categorise the spectral data in the region of interest (1700-1500cm(-1)) containing the carboxylate (COO(-)) asymmetric stretching vibrations of DF Na. Spectral data showed the redshifts of the COO(-) asymmetric stretching vibrations for DF Na in the solution compared with solid drug. Similar shifts were evident following application of saturated solutions of DF Na to porcine skin samples. Multivariate data analysis categorised the spectral data based on the spectral differences and drug crystallisation was found to be confined to the upper layers of the skin. This proof-of-concept study highlights the utility of ATR-FTIR spectroscopy in combination with multivariate data analysis as a simple and rapid approach in the investigation of drug deposition in the skin. The approach described here will be extended to the study of other actives for topical application to the skin.
A truncated form of an α-amylase, GTA, from thermophilic Geobacillus thermoleovorans CCB_US3_UF5 was biochemically and structurally characterized. The recombinant GTA, which lacked both the N- and C-terminal transmembrane regions, functioned optimally at 70°C and pH 6.0. While enzyme activity was not enhanced by the addition of CaCl2, GTA's thermostability was significantly improved in the presence of CaCl2. The structure, in complex with an acarbose-derived pseudo-hexasaccharide, consists of the typical three domains and binds one Ca(2+) ion. This Ca(2+) ion was strongly bound and not chelated by EDTA. A predicted second Ca(2+)-binding site, however, was disordered. With limited subsites, two novel substrate-binding residues, Y147 and Y182, may help increase substrate affinity. No distinct starch-binding domain is present, although two regions rich in aromatic residues have been observed. GTA, with a smaller domain B and several shorter loops compared to other α-amylases, has one of the most compact α-amylase folds that may contribute greatly to its tight Ca(2+) binding and thermostability.
Red mud as industrial waste from bauxite was utilized as a precursor for the synthesis of mesoporous ZSM-5. A high concentration of iron oxide in red mud was successfully removed using alkali fusion treatment. Mesoporous ZSM-5 was synthesized using cetyltrimethylammonium bromide (CTABr) as a template via dual-hydrothermal method, and the effect of crystallization time was investigated towards the formation of mesopores. Characterization using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N2 adsorption-desorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated the formation of cubic crystallite ZSM-5 with high surface area and mesopore volume within 6 h of crystallization. Increasing the crystallization time revealed the evolution of highly crystalline ZSM-5; however, the surface area and mesoporosity were significantly reduced. The effect of mesoporosity was investigated on the adsorption of methylene blue (MB). Kinetic and thermodynamic analysis of MB adsorption on mesoporous ZSM-5 was carried out at a variation of adsorption parameters such as the concentration of MB solution, the temperatures of solution, and the amount of adsorbent. Finally, methanol, 1-butanol, acetone, hydrochloric acid (HCl), and acetonitrile were used as desorbing agents to investigate the reusability and stability of mesoporous ZSM-5 as an adsorbent for MB removal.
Solution-mediated transformation has been cited as one of the main problems that deteriorate dissolution performances of solid dispersion (SD). This is mainly attributed by the recrystallization tendency of poorly soluble drug. Eventually, it will lead to extensive agglomeration which is a key process in reducing the dissolution performance of SD and offsets the true benefit of SD system. Here, a post-processing treatment is suggested in order to reduce the recrystallization tendency and hence bring forth the dissolution advantage of SD system.