Advances in our understanding of the structure and functionality of edible fats and fat mimetics.

The reasons for the increased world-wide incidence of obesity, type-2 diabetes, and cardiovascular disease include sedentary lifestyles and poor food choices. Regulatory agencies in several countries now require companies to add unattractive front of package labels to their products where salt, sugar and fat (or saturated fat) levels are prominently displayed. After the demise of partially hydrogenated fats, saturated fat has become the new target. Consumption of saturated fat over polyunsaturated oil has been clearly shown to increase cholesterol levels in humans. However, saturated fats provide the functionality required in many food products. To complicate matters, concerns over sustainability, veganism, genetically modified organisms, animal welfare, as well as religious beliefs, severely limit our sources of saturated fat. In this review we will discuss recent advances in our understanding of the nano and mesoscale structure of fats, responsible for their physical functionality and contrast it to that of fat mimetics. Fat mimetics include polymeric networks of ethylcellulose, emulsion-templated networks of proteins and polysaccharides, colloidal and self-assembled fibrillar networks of polar lipid crystals, as well as solid o/w emulsions of oil trapped within crystallized lamellar mesophases. Clean label and economic considerations will also be touched upon.

Unsaturated emulsifier-mediated modification of the mechanical strength and oil binding capacity of a model edible fat crystallized under shear.

The effects of processing using a scraped surface heat exchanger (SSHE) before and after adding unsaturated monoglyceride (UM) on blends of fully hydrogenated soybean oil (FHSO) and soybean oil (SO) were studied. Mixtures of 40:60 and 45:55 FHSO:SO were melted at 80 °C for 30 min and crystallized statically or in the SSHE (shear rate of 25 s(-1)) at a cooling rate of 9 °C/min. Upon shearing and UM addition, polymorphic transformations toward more (ß) or less (ß') stable forms were governed by the combination between system concentration, composition, and crystallization conditions, as determined by differential scanning calorimetry and powder X-ray diffraction. Nuclear magnetic resonance was used to measure the solid fat content (SFC) development which showed to increase with processing conditions due to the high nucleation rate induced. Processing conditions greatly affected the nano- and microcrystalline structures which were characterized by polarized light microscopy (PLM), cryogenic transmission electron microscopy (Cryo- TEM), and Scherrer analysis of the powder X-ray diffraction data. Crystallization under shear promoted the longitudinal growth of the nanoplatelets; nevertheless, meso structural elements showed a decrease in their dimensions under the same crystallization conditions. The relative oil loss determined gravimetrically was inversely related to the elastic modulus and yield stress of the sheared fat blends, and values were closer to the desirable usability ranges for bakery applications. Our results suggest that fully hydrogenated fats can be functionalized by crystallization in a SSHE and/or by judicious addition of an unsaturated emulsifier.

Evaluation of Pure Bile Salts in Place of Bile Extract in the Standardized INFOGEST Digestion Protocol for Quantification of Sterol Bioaccessibility.

Improving standardized in vitro digestion protocols for phytosterols (PSs) is critical for understanding their bioaccessibility (BA) in food products and supplements. In this study, in vitro BA of phytosterol esters (PSEs) and free cholesterol (Ch) was compared under modified digestion conditions. The addition of Ch esterase (CE) to the INFOGEST model containing bovine bile resulted in a 70% increase in PS BA and an 18.5% reduction in Ch micellarization. Relative to the standardized INFOGEST model, substitution of pure bile salts (PBSs) did not significantly change PS BA or Ch micellarization. In the presence of CE, the substitution resulted in a 49.9% reduction in PS BA and a 13% increase in Ch micellarization. The differing results may be due to inhibitory effects of PBSs on the activity of intestinal enzymes, including CE. These results suggest that the INFOGEST model should include Ch esterase and the continued use of bile extract to evaluate PS BA.

Novel biphasic gels can mimic and replace animal fat in fully-cooked coarse-ground sausage.

Four biphasic gels (BPG) were developed and tested as pork fat replacers in coarse-ground fully-cooked sausages. An oleogel (OG) phase (92.5% high-oleic soybean oil, 7.5% rice bran wax) and one of two hydrogel (HG) phases (water and 7% or 8% gelatin) were combined in 7:3 or 6:4 OG:HG ratios, for a total of four test formulations. Control sausages were formulated to 27.5% fat and stored at 0-2 °C for 98 d. BPGs allowed for fat reductions of up to 26%. Visually, all BPGs resembled pork fat. There were no differences in external L* and a* but, internally, controls were darker and redder. Except for one control, there were no differences in Texture Profile Analysis (TPA) hardness, cohesiveness, springiness, and chewiness. Warner-Bratzler Shear (WBS) force was highest in 6:4 samples, which were also highest in Sensory First Bite Firmness and lowest in Smoked Sausage Aroma and Smoked Sausage Flavor. TBARS values remained steady, with no rancid flavors detected by the sensory panel.

Synergistic effects of starch nanoparticles and chitin nanofibers on the stability of oil-in-water Pickering emulsions.

Starch nanoparticles (SNPs) and Chitin nanofibers (ChFs) have been recognized to be effective for emulsion stabilization. Hence, the use of multiple solid nanoparticles seems to be a promising approach to improve emulsion stability. This work aims to studyemulsions stabilized by a combination of SNPs and ChFs at different concentrations over storage time and different environmental conditions. Sonicated emulsions were found to have a significantly higher stability compared to non-sonicated emulsions. Furthermore, SNP/ChF-stabilized emulsions showed smaller droplet sizes and higher stability within a wide range of temperatures and pH, suggesting a synergistic effect between both particles as stabilizers. The addition of NaCl showed limited impact, particularly in concentrations up to 200 mM, on the improvement of the stability of emulsions. The combined use of SNPs and ChFs allowed emulsion stabilization at lower solid nanoparticles concentrations than when only either SNPs or ChFs were used.

Curcumin encapsulation in Pickering emulsions co-stabilized by starch nanoparticles and chitin nanofibers.

This study examined the stability and release of curcumin encapsulated in Pickering emulsions stabilized by starch nanoparticles and chitin nanofibers under different conditions. Curcumin stability under UV exposure and the release of curcumin from Pickering emulsions in excess water were evaluated over 24 h; while the storage stability of curcumin was assessed over 16 d. The amount of curcumin remaining in the emulsions was quantified spectrophotometrically to characterize its stability and kinetics of release. The progress of lipid oxidation was also monitored by determining peroxide (PV) and p-anisidine (AV) values. The results of passive release measurements indicated over 60% of curcumin was retained after 24 h. SNP/ChF-stabilized Pickering emulsions showed approximately 50% and 45% of curcumin retention upon 16 d of storage and under UV exposure, respectively. Moreover, significant improvement in the curcumin retention was found when higher concentrations of both solid nanoparticles were used. The degradation kinetics of curcumin over storage time and under UV exposure were found to follow first order kinetics. When both emulsifiers were doubled (C4S2), shelf-life was extended to longer than 60 d (AV < 10). This study provides a promising approach to protect encapsulated curcumin, which could potentially be used in functional food products with extended shelf-life.

Correction: Curcumin encapsulation in Pickering emulsions co-stabilized by starch nanoparticles and chitin nanofibers.

[This corrects the article DOI: 10.1039/D1RA01622A.].

Development of methylcellulose-based sustained-release dosage by semisolid extrusion additive manufacturing in drug delivery system.

The objective of this study is to fabricate customized dosage forms using extrusion-based 3D printing for the sustained delivery of theophylline. The therapeutic paste was prepared by combining various doses of theophylline (0, 75, 100, and 125 mg) with different concentrations of methylcellulose (MC) A4M (8, 10, and 12%). The paste was then 3D printed into semisolid tablets under optimized printing conditions. The rheological properties of printing pastes were related to the 3D printability. Our results indicated that to be 3D printed using the current platform, the storage modulus (G') of the printing paste should be higher than the loss modulus (G″) during the frequency sweep (0.1-600 rad/s), and the tan δ should fall in the range of 0.25-0.27 at 0.63 rad/s. The printed tablets formulated with 10% MC showed the highest overall quality, considering the aspects of resolution, texture, and shape retention regardless of the dosage. The scanning electron microscopy images indicated that the cross-linked structure of MC A4M formed the microscale porous microstructure, which has the potential to embed the theophylline, thus delayed the release through the barrier effect. The in vitro dissolution test revealed that the 3D printed tablets exhibited a sustained release during the first 12 hr. The findings in this study will support the development of customized, personalized medicine with improved efficacy.

Role of supramolecular policosanol oleogels in the protection of retinyl palmitate against photodegradation.

Exposure of retinyl palmitate (RP) to ultraviolet radiation can lead to its photo-degradation and loss of biological activity. Therefore, there is a demand to explore new approaches to protect RP in an easy, economical and efficient way. The objective of this study was to explore the role of policosanol oleogels (PCOs) in the protection of RP from photodegradation. UV-blocking action was tested by placing a layer of PCO as a barrier between a UVA (365 nm) source and 1% RP in soybean oil. Effects of structural characteristics of PCOs cooled at different rates on RP photostability were also studied. The ability of PCOs to prevent radical-mediated reactions was assessed by measuring oil oxidative stability over storage time at 40 °C. The remaining % RP was measured by HPLC during 4 days of UVA irradiation. PCO blocked energy absorption from UVA and further dampened the UVA mediated ionic photodissociation and free radical reactions due to matrix immobilization. After 4 days of UV exposure, photodegradation of RP was reduced by 64% when a PCO layer was used as a barrier. Peroxide values (PV) and p-anisidine values (p-A.V.) of soybean oil (SO) were significantly higher than those of PCOs over storage time. Cooling rate processing played a significant role in RP protection; the faster the cooling rate, the higher the RP photostability. This study demonstrated that the protective mechanism of RP in PCOs is a combined effect of physical UV-barrier action, molecular immobilization and inhibition of the free radical-mediated reaction.

Effects of pre-heating soybean protein isolate and transglutaminase treatments on the properties of egg-soybean protein isolate composite gels.

The objective of this study was to determine the effects of pre-heating soybean protein isolate (SPI) and transglutaminase (TG) induced cross-linking on egg-SPI composite gels. Solubility, surface hydrophobicity, electrophoresis and rheology of the prepared solutions were determined, whereas texture, water-holding capacity and microstructure of the composite gels were evaluated. SPI pre-heating improved solutions' solubility and protein's surface hydrophobicity; thus enhancing TG cross-linking evidenced by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). When only TG was used, solubility and surface hydrophobicity of the composites remained unchanged or decreased, forming strong gels but with low springiness and water-holding capacity. When SPI pre-heating and TG action were combined, a denser and finer gel network was obtained that exhibited improved mechanical properties and better water-holding capacity. The results of this research demonstrate that the combination of pre-heating SPI and TG treatment is a reliable method to improve the gelling properties of egg-SPI composite gels.

3D printing of extended-release tablets of theophylline using hydroxypropyl methylcellulose (HPMC) hydrogels.

An extrusion based 3D printer was used to prepare the semi-solid tablets with different drug loading dosages (75, 100, 125 mg) under ambient temperature. The active pharmaceutical ingredient, theophylline, was uploaded within the hydrogels prepared of hydroxypropyl methylcellulose (HPMC) K4M or E4M. The HPMC concentrations were adjusted to different levels (10 and 12% w/w) to fulfill the requirements for 3D printing. Rheological and textural properties, as well as release profiles, were significantly affected by the type and concentration of excipient regardless of theophylline doses used. The printing material should exhibit shear-thinning behavior, keeping yield stress less than 4000 Pa and a loss factor (tanδ = G''/G') between 0.2 and 0.7, especially for 3D printing purposes using the current platform. The SEM images demonstrated that the hydrogel matrix exhibited a porous structure, which had the potential to encapsulate the theophylline clusters within its microstructure. The in vitro dissolution test showed that the release of all tablets was extended over 12 h, and the calculation of drug release kinetic models revealed that the 3D printed HPMC matrices release the theophylline by diffusion and erosion mechanisms. The excipient HPMC K4M 12% w/w hydrogel was optimal to load the theophylline with flexible dosage combinations due to the great extrudability and shape retention ability. The exploration of rheological properties was investigated in this study, and the results revealed that it is a feasible method to predict the SSE 3D printability and quality of hydrogel-API blend materials for the drug delivery system.

Rheological characteristics of mechanically separated chicken and chicken breast trim myofibril solutions during thermal gelation.

Mechanically separated chicken (MSC) was obtained by two different separation methods (MSC1, Beehive separator, 3-5 d-old bones; MSC2, Poss separator, fresh bones) and compared to chicken breast trim (CBT). Rheological attributes of myofibrillar protein solutions during thermal gelation and cooling were evaluated. All sources exhibited gelation with increased temperature (decreased δ). In all three treatments, a peak, decline, and subsequent increase in both the G' and G″ was observed in the 50-55 °C range, with peak values being higher for CBT than for both MSCs. G' slopes on both sides of the peak (S2, S3) and following the decline (S4) were significantly different between CBT and both MSCs (P < 0.05) and indicated greater instability of the solid-like structure in the temperature range of 50-55 °C (myosin rod denaturation). Myofibrillar protein profiles confirmed fiber type differences among materials, as well as greater myosin fragmentation or modification in the MSC samples.

Development of lecithin and stearic acid based oleogels and oleogel emulsions for edible semisolid applications.

The objective of this study was to characterize a novel soy lecithin (SL) based oleogel (LOG) and oleogel emulsion (LOGE) prepared with different proportions of stearic acid (SA). Oleogels were developed with 1 wt% of water, and two gelator concentrations (20 wt% and 30 wt%) with SL:SA ratios (0:10, 3:7, 5:5, 7:3, 10:0). The same SL:SA proportions were used to prepare LOGE with 10 wt% and 20 wt% of water. Small (SAXD) and wide (WAXD) angle x-ray diffraction studies and polarized light microscopy were conducted to determine the nano- and microstructure of the samples. The hardness of the samples was analyzed using a texture analyzer and the thermal properties with a differential scanning calorimeter. The results indicate that LOG were primarily formed through the entanglement of bundles of reverse worm-like micelles of SL; however, LOGE were structured mainly through SA crystals that interacted in a synergistic fashion with the SL reverse micelles network to stabilize the three dimensional network. The hardness of the LOG and LOGE increased with an increase in SA, however, in samples containing both SL and SA, LOGE were harder than LOG, demonstrating that the oleogelators have a synergistic effect. The novel hybrid LOG and LOGE formulated with SA can be used as a more stable alternative to SL oleogels particularly when the objective is to achieve semi-solid characteristics.

Non-enzymatic browning kinetics analysed through water-solids interactions and water mobility in dehydrated potato.

Non-enzymatic browning (NEB) development was studied in dehydrated potato at 70°C. It was related to the macroscopic and molecular properties and to water-solid interactions over a wide range of water activities. Time resolved (1)H NMR, thermal transitions and water sorption isotherms were evaluated. Although non-enzymatic browning could be detected in the glassy state; colour development was higher in the supercooled state. The reaction rate increased up to a water content of 26g/100g of solids (aw=0.84) and then decreased at higher water contents, concomitantly with the increase of water proton mobility. The joint analyses of NEB kinetics, water sorption isotherm and proton relaxation behaviour made it evident that the point at which the reaction rate decreased, after a maximum value, could be related to the appearance of highly mobile water. The results obtained in this work indicate that the prediction of chemical reaction kinetics can be performed through the integrated analysis of water sorption, water and solids mobility and the physical state of the matrix.

Use of Reconstitued Yolk Systems To Study the Gelation Mechanism of Frozen-Thawed Hen Egg Yolk.

Yolk gelation upon 5 week freezing-thawing was studied in four recombined yolk systems containing different plasma and granule proportions. Fractionation for mass distribution, sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) for protein distribution, and rheological properties were explored. Results indicate that both plasma and granule components, including low-density lipoprotein (LDL), high-density lipoprotein (HDL), and α-livetin proteins, contributed to gelation. Protein aggregation was reflected through a large mass increase in the granule fraction and appearance of a floating LDL layer upon fractionation of gelated yolk systems. A significant increase in gel strength (elastic modulus, G') was observed with the increase of the granule content. Overall, this study provides a better understanding of yolk gelation mechanism that may consequently lead to the design of innovative methods for preventing gelation. A schematic presentation of the yolk gelation mechanism is also proposed.

Kinetic study on photostability of retinyl palmitate entrapped in policosanol oleogels.

Photostability of all-trans retinyl palmitate (RP) (100% bioactivity) was studied in policosanol oleogels (PCOs) (7-12% w/w policosanol in soybean oil) after UVA irradiation. RP was incorporated into PCOs at levels of 0.04%, 0.1% and 1% (w/w). PCOs efficiently protected RP from UVA-mediated degradation. Over 75% RP-activity remained in PCOs after 4 days of UVA irradiation, while 12% RP-activity remained in soybean oil. HPLC analysis showed that cis-RP was formed in liquid soybean oil after 2 days of UVA irradiation while it was absent in PCOs matrices. PCOs blocked the energy absorption from UVA and further dampened the UVA-mediated ionic photodissociation and free radical reaction due to matrix immobilization. For all samples, RP photodegradation followed a 2nd order reaction. From the reaction kinetics, it would be possible to predict the RP photodegradation rate in PCO matrices. PCOs were shown to be a promising matrix to protect RP from photodegradation.

Replacement of pork fat in frankfurter-type sausages by soybean oil oleogels structured with rice bran wax.

The objective of this study was to assess the impact of replacing pork backfat with rice bran wax oleogels on the organoleptic properties of frankfurter-type finely-comminuted sausages. Frankfurters were formulated using the following treatments as lipid replacement: 1) pork fat (PF); 2) soybean oil (SBO); 3) 2.5% rice bran wax oleogel (2.5 RBW); 4) 10% rice bran wax oleogel (10 RBW); and 5) 2.5% rice bran wax oleogel sheared less during frankfurter production (RBW/LS). In general, control PF was darker and redder than other treatments. TPA revealed oleogel treatments to be similar (P > .05) to pork fat treatment for firmness, chewiness, and springiness. Additionally, sensory evaluation revealed that replacing pork fat did not influence cured frankfurter aroma, but cured frankfurter flavor was significantly reduced (P < .05). Furthermore, lipid oxidation significantly (P < .05) differed between PF and 10 RBW. The results show that rice bran wax oleogels have the potential to successfully replace pork fat in comminuted products.

In Situ Self-Assembled Nanocomposites from Bacterial Cellulose Reinforced with Eletrospun Poly(lactic acid)/Lipids Nanofibers.

The goal of this study is to explore a new strategy to improve the mechanical and hydrophobic properties of bacterial cellulose (BC) mats. The present work is the first to report the preparation of in situ self-assembled BC nanocomposites using electrospun hydrophobic poly(lactic acid) (PLA) or PLA/lipids (PLA/Lip) nanofiber mats as foundation for BC nanofiber growth. Adding electrospun PLA mats to the BC culture media led to a two-fold increase in toughness with a 52% increase in elongation of the nanocomposites with regard to BC. The incorporation of electrospun PLA and PLA/Lip nanofiber mats lowered the moisture regain and water vapor transmission of BC nanocomposites relative to pure BC mats. The interfacial bonding between the individual components of a nanocomposite is a key factor for the improvement of composite strength, stiffness, and barrier properties; thus additional strategies to improve interaction between hydrophilic BC and hydrophobic PLA fibers need to be explored.

Analysis of co-crystallized free phytosterols with triacylglycerols as a functional food ingredient.

This research focuses on the analysis of mixtures of free phytosterols (FPSs) with fully hydrogenated soybean oil (FHSO):soybean oil (SO) mixtures as a potential zero-trans substitute for various types of shortenings. Oil binding capacity as well as the thermal, rheological and structural properties of FHSO:SO blends containing 0, 20 and 25wt.% ß-sitosterol or stigmasterol were investigated in this study. Differential interference contrast (DIC) microscopy and wide angle X-ray diffraction (WAXRD) revealed that co-crystallization of FPSs with FHSO:SO blends occurred. Polymorphic forms were characterized as a mixture of ß' and ß for all samples. The addition of FPSs decreased oil loss (OL) of FHSO:SO samples. Melting profiles of the prepared FPS-TAG (triacylglycerol) blends were extended to higher temperatures compared to a commercial shortening. Rheological properties were comparable to those of commercial puff pastry shortening suggesting that FPS-TAG blends may be acceptable for bakery applications. FPSs co-crystallized with FHSO and SO may be a suitable trans-fat free substitute for a number of types of shortening, including puff pastry shortening. The manufacturing of co-crystallized /FPS-TAG matrices will possibly bring large economic benefits as their functionalization can potentially be achieved by using existing simple shear processing.

Development of a low resolution (1)H NMR spectroscopic technique for the study of matrix mobility in fresh and freeze-thawed hen egg yolk.

Three experiments were conducted in developing a low resolution proton nuclear magnetic resonance ((1)H NMR) spectroscopic technique to study matrix mobility in fresh and freeze-thawed gelled yolk. The Carr-Purcell-Meiboom-Gill (CPMG) sequence was used to measure spin-spin relaxation times of proton pools representing major yolk constituents. A component identification test distinguished 3-4 pools. The least mobile pool was assigned to proteins, protein-lipid and protein-water interactions, and the most mobile to unbound water. The remaining pools were assigned to lipids, lipid-protein and lipid-water interactions. A stability test indicated that yolk had varied matrix mobility within the same sample across five days of refrigeration storage. A reproducibility test demonstrated high repeatability of fresh yolk measurements, but significant differences (p<0.05) were found within gelled yolk samples. This research determined that (1)H NMR spectroscopy, a non-destructive technique, can identify yolk components and detect changes in the matrix.