Novel palm shortening substitute using a combination of rapeseed oil, linseed meal and beta-glucan.

This study investigated the potential of a novel sustainable ingredient composed of rapeseed oil, linseed meal and beta-glucan (PALM-ALT) to mimic palm shortening functionality in cake. The combined functional properties of linseed meal and beta-glucan led to stable semi-solid emulsion-gels (20-31 µm oil droplet size, 105-115 Pa.s viscosity and 60-65 Pa yield stress). PALM-ALT contained 25 and 88% less total and saturated fat than palm shortening, whilst PALM-ALT cakes contained 26 and 75% less total and saturated fat than the palm-based control. PALM-ALT cakes matched the flavour profile of the palm-based control, while rapeseed oil cakes tasted more sour and less sweet than the control (p < 0.05). PALM-ALT cakes proved less hard and more cohesive than the control (p < 0.05), with 100% of the consumer panel preferring PALM-ALT formulations. This study demonstrated the unique potential of PALM-ALT as healthier, sustainable and competitive alternative to palm shortening.

Atomic Force Microscopy of Phytosterol Based Edible Oleogels.

This work reviews the use of atomic force microscopy (AFM) as a tool to investigate oleogels of edible triglyceride oils. Specific attention is given to those oleogels based on phytosterols and their esters, a class of material the authors have studied extensively. This work consists of a summary of the role of AFM in imaging edible oleogels, including the processing and preparation steps required to obtain high-quality AFM images of them. Finally, there is a comparison between AFM and other techniques that may be used to obtain structural information from oleogel samples. The aim of this review is to provide a useful introduction and summary of the technique for researchers in the fields of gels and food sciences looking to perform AFM measurements on edible oleogels.

Mycoprotein as novel functional ingredient: Mapping of functionality, composition and structure throughout the Quorn fermentation process.

This study provides the first mapping of mycoprotein functionality, composition and structure throughout the Quorn fermentation process. The fermentation broth, RNA-reduced broth (RNA-broth), centrate and their centrifugation deposits and supernatants were characterised. The broth, RNA-broth and their deposits displayed high concentrations of fungal filaments, which contributed to their high gelling properties (with a 5,320 Pa elastic modulus reported for RNA-broth deposits gels). Foams prepared with RNA-broth and centrate supernatants via frothing exhibited high stability (380 min), with high concentrations of a foam-positive cerato-platanin reported in these samples. Emulsions prepared with the broth and broth supernatant showed high emulsifying activity and stability indexes (12.80 m2/g and 15.84 mins for the broth supernatant) and low oil droplet sizes (18.09 µm for the broth). This study identified previously unreported gelling, foaming and/or emulsifying properties for the different Quorn streams, highlighting opportunities to develop novel sustainable alternatives to animal-derived functional ingredients using mycoprotein material.

Phase Behaviour, Functionality, and Physicochemical Characteristics of Glycolipid Surfactants of Microbial Origin.

Growing demand for biosurfactants as environmentally friendly counterparts of chemically derived surfactants enhances the extensive search for surface-active compounds of biological (microbial) origin. The understanding of the physicochemical properties of biosurfactants such as surface tension reduction, dispersion, emulsifying, foaming or micelle formation is essential for the successful application of biosurfactants in many branches of industry. Glycolipids, which belong to the class of low molecular weight surfactants are currently gaining a lot of interest for industrial applications. For this reason, we focus mainly on this class of biosurfactants with particular emphasis on rhamnolipids and sophorolipids, the most studied of the glycolipids.

Exploring how changes to the steroidal core alter oleogelation capability in sterol: γ-oryzanol blends.

Oleogels based on sterols such as ß-sitosterol blended with the sterol ester γ-oryzanol are a very interesting class of systems, but there are aspects of their formation and structure that remain elusive. It has previously been shown that a methyl group on the C30 position of the sterol-ester plays an important role in gelation. This work explored the effect that having C30 methyl groups on both the sterol and the sterol-ester had on the gelation process and subsequent gel structure. Lanosterol and saponified γ-oryzanol (which was synthesized as part of this study) were identified as materials of interest, as both feature a methyl group on the C30 position of their steroidal cores. It was observed that both sterols formed gels when blended with γ-oryzanol, and also that lanosterol gelled sunflower oil without the addition of γ-oryzanol. All of these gels were significantly weaker than that formed by ß-sitosterol blended with γ-oryzanol. To explore why, molecular docking simulations along with AFM and SAXS were used to examine these gels on a broad range of length scales. The results suggest that saponified γ-oryzanol-γ-oryzanol gels have a very similar structure to that of ß-sitosterol-γ-oryzanol gels. Lanosterol-γ-oryzanol gels and pure lanosterol gel, however, form with a totally different structure facilitated by the head-to-tail stacking motif exhibited by lanosterol. These results give further evidence that relatively slight changes to the molecular structure of gelators can result in significant differences in subsequent gel properties.

Toxicity Profiling of Biosurfactants Produced by Novel Marine Bacterial Strains.

Surface active agents (SAAs), currently used in modern industry, are synthetic chemicals produced from non-renewable sources, with potential toxic impacts on humans and the environment. Thus, there is an increased interest for the identification and utilization of natural derived SAAs. As such, the marine environment is considered a promising source of biosurfactants with low toxicity, environmental compatibility, and biodegradation compared to their synthetic counterparts. MARISURF is a Horizon 2020 EU-funded project aiming to identify and functionally characterize SAAs, derived from a unique marine bacterial collection, towards commercial exploitation. Specifically, rhamnolipids produced by Marinobacter MCTG107b and Pseudomonas MCTG214(3b1) strains were previously identified and characterized while currently their toxicity profile was assessed by utilizing well-established methodologies. Our results showed a lack of cytotoxicity in in vitro models of human skin and liver as indicated by alamar blue and propidium iodide assays. Additionally, the use of the single gel electrophoresis assay, under oxidative stress conditions, revealed absence of any significant mutagenic/anti-mutagenic potential. Finally, both 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulphonicacid) (ABTS) and 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) cell-free assays, revealed no significant anti-oxidant capacity for neither of the tested compounds. Consequently, the absence of significant cytotoxicity and/or mutagenicity justifies their commercial exploitation and potential development into industrial end-user applications as natural and environmentally friendly biosurfactants.

Congener-dependent conformations of isolated rhamnolipids at the vacuum-water interface: A molecular dynamics simulation.

HYPOTHESIS: Molecular dynamics simulation can be used to differentiate between the adsorption properties of rhamnolipid congeners at a vacuum-water interface. EXPERIMENTS: Adsorption of five congeners with differing alkyl chains (two C10 chains, two C14 chains or mixed C14C10 and C10C14), number of rhamnose rings (mono- or di-) and carboxyl group charge (non-ionic or anionic) are simulated at the vacuum-water interface. FINDINGS: All rhamnolipids adsorb in the interfacial region with rhamnose and carboxyl groups closer to the water phase, and alkyl chains closer to the vacuum phase, but with differing adsorbed conformations. Headgroups of uncharged congeners show two preferred conformations, closed and partially open. Di-rhamnolipid has a low proportion of closed conformation, due to the steric constraints of the second pyranose ring. Charged congeners show strong preference for closed headgroup conformations. For rhamnolipids with equal alkyl chains lengths (C10C10, C14C14) the distribution of alkyl chain tilt angles is similar for both. Where chain lengths are unequal (C14C10, C10C14) one chain has a greater tendency to tilt towards the water phase (>90°). The order parameter of the alkyl chains shows they are disordered at the interface. Together, these results show congener-dependent adsorbed conformation differences suggesting they will have differing surface-active properties at vacuum-water and oil-water interfaces.

Coassembly of C13-Dipeptides: Gelations from Solutions and Precipitations.

C13-dipeptides that did not gel on their own were found to form hydrogels when combined with mixtures (coassembly). At pH = 4.6, by mixing negatively charged C13-WD (C13-WD2- and/or C13-WD-) with C13-KW or C13-YK, where the side chain of K carried positive charge, two composite hydrogels with different mechanical properties were formed. The gels exhibited various fiber structures that would account for their individual functionalities. According to molecular dynamics computer simulations, the composite systems formed spherical micelles through hydrophobic interactions that further aggregate to form gels through electrostatic interactions. The electrostatic repulsions between C13-WD molecules were interfered by insertions of C13-KW or C13-YK molecules, which result in gel formation in the composite systems. The results of computer simulations well explained the experimental observations, which provided new insights into the design and selection strategies for peptide gelators.

Surface Active Agents and Their Health-Promoting Properties: Molecules of Multifunctional Significance.

Surface active agents (SAAs) are molecules with the capacity to adsorb to solid surfaces and/or fluid interfaces, a property that allows them to act as multifunctional ingredients (e.g., wetting and dispersion agents, emulsifiers, foaming and anti-foaming agents, lubricants, etc.) in a widerange of the consumer products of various industrial sectors (e.g., pharmaceuticals, cosmetics, personal care, detergents, food, etc.). Given their widespread utilization, there is a continuously growing interest to explore their role in consumer products (relevant to promoting human health) and how such information can be utilized in order to synthesize better chemical derivatives. In this review article, weaimed to provide updated information on synthetic and biological (biosurfactants) SAAs and their health-promoting properties (e.g., anti-microbial, anti-oxidant, anti-viral, anti-inflammatory, anti-cancer and anti-aging) in an attempt to better define some of the underlying mechanism(s) by which they exert such properties.

Investigating the biomolecular interactions between model proteins and glycine betaine surfactant with reference to the stabilization of emulsions and antimicrobial properties.

Binding effect and interaction of 2-pentadecanoyloxymethyl)trimethylammonium bromide (DMGM-14) with bovine serum albumin (BSA) and hen egg white lysozyme (HEWL) were systematically investigated by the fluorescence spectroscopy, circular dichroism (CD) spectroscopy, isothermal titration calorimetry (ITC), surface tension analysis, and molecular docking studies. The emulsion properties and particle size distribution of surfactant/protein complexes containing sunflower oil were studied using static light scattering and confocal laser scanning microscopy (CLSM). The fluorescence spectroscopy and ITC analysis confirmed the complexes formation of DMGM-14 with BSA and HEWL which was also verified by surface tension measurements. CD results explained the conformational changes in BSA and HEWL upon DMGM-14 complexation. Molecular docking study provides insight into the binding of DMGM-14 into the specific sites of BSA and HEWL. Besides, the studies drew a detailed picture on the emulsification properties of DMGM-14 with BSA and HEWL. In addition, the in vitro experiment revealed a broad antibacterial spectrum of DMGM-14 and DMGM-14/HEWL complex including activity against Gram-positive and Gram-negative bacteria. In conclusion, the present study revealed that the interaction between DMGM-14 with BSA and HEWL is important for the pharmaceutical, biological, and food products.

Marine-Derived Surface Active Agents: Health-Promoting Properties and Blue Biotechnology-Based Applications.

Surface active agents are characterized for their capacity to adsorb to fluid and solid-water interfaces. They can be classified as surfactants and emulsifiers based on their molecular weight (MW) and properties. Over the years, the chemical surfactant industry has been rapidly increasing to meet consumer demands. Consequently, such a boost has led to the search for more sustainable and biodegradable alternatives, as chemical surfactants are non-biodegradable, thus causing an adverse effect on the environment. To these ends, many microbial and/or marine-derived molecules have been shown to possess various biological properties that could allow manufacturers to make additional health-promoting claims for their products. Our aim, in this review article, is to provide up to date information of critical health-promoting properties of these molecules and their use in blue-based biotechnology (i.e., biotechnology using aquatic organisms) with a focus on food, cosmetic and pharmaceutical/biomedical applications.

A Comprehensive Study on Self-Assembly and Gelation of C13-Dipeptides-From Design Strategies to Functionalities.

Computational and experimental methods were applied to investigate the self-assembly and gelation of C13-dipeptides. A modified aggregation propensity (APS) was introduced to correlate the effects of side chains of amino acids on the tendency to aggregate. From the experimental results, the ranges of 0.156 < APS < 0.250 seemed to be a proper region for the C13-dipeptides to form hydrogels, while other molecules with higher or lower APS were insoluble or dissociated. As observed from molecular dynamics simulations, the C13-dipeptides first formed small aggregates through hydrophobic interactions and then rearranged through electrostatic attractions and hydrogen bonds for self-assembly. The C13-dipeptides tended to be antiparallel packed, as shown by hydrogen bonding analyses. Experimental observations and analyses on the structures of C13-dipeptide hydrogels matched the computational conclusions very well. From the five selected gelators, i.e., C13-GW, C13-VY, and C13-WT, strong π-π stacking was observed. For C13-WS, strong hydrogen bonding was found, and in C13-WY, both strong π-π interactions and hydrogen bonds were found. It takes around 90 min or longer for C13-dipeptides to form hydrogels, and those formed by C13-WY and C13-WS had weak water holding capacities, which might be due to strong intermolecular hydrogen bonding. From rheological studies, the C13-dipeptides formed strong chemical gels that were stabilized by strong interactions between the molecular aggregates. These gelators exhibit the potentials to be environmentally friendly substitutes for the common functionalized peptide gelators.

Interfacial ordering of tristearin induced by glycerol monooleate and PGPR: A coarse-grained molecular dynamics study.

We use coarse-grained molecular dynamics simulations to study the effect of surfactant structure on the ordering of bulk tristearin at an oil-water interface. In the absence of surfactant, tristearin acyl chains are marginally aligned normal to the interface. The surfactant glycerol monooleate (GMO), a common small-molecule monoacylglycerol (MW: 357 g/mol), preferentially adsorbs to the oil-water interface, displacing more of the tristearin as its concentration increases. The tristearin that remains at the interface is closely aligned normal to the interface. Adjacent to the interface, bulk tristearin increasingly aligns with its acyl chains entwined with the GMO acyl chain, which also preferentially aligns normal to the interface. In contrast, polyglycerol polyricinoleate (PGPR), a bulkier, polymeric surfactant (MW: 1398 g/mol for a molecule with five monomers), both displaces tristearin from the interface and reduces the alignment of the molecules that remain. We suggest that the similar fatty acid moieties of GMO (oleic acid) and tristearin (stearic acid) lead to liquid-state association and alignment, the latter of which can then serve as a template onto which tristearin crystals can nucleate. Conversely, by both displacing tristearin from the interface and reducing alignment below that of the surfactant-free system, PGPR eliminates the possibility of tristearin interfacial crystallisation.

Molecular Interactions behind the Self-Assembly and Microstructure of Mixed Sterol Organogels.

In this work, we have employed docking and atomistic molecular dynamics (MD) simulations supported by complementary experiments using atomic force microscopy, rheology, and spectroscopy to investigate the self-assembled structure of ß-sitosterol and γ-oryzanol molecules into cylindrical tubules in a nonaqueous solvent. Docking models of several phytosterols, including sitosterol, with oryzanol and other sterol esters demonstrate that for systems to form tubules, the phytosterol sterane group must be stacked in a wedge shape with the ester sterane group and a hydrogen bond must form between the hydroxyl group of the phytosterol and the carbonyl group of the ester. MD of the self-assembled structure were initiated with the molecules in a roughly cylindrical configuration, as suggested from previous experimental studies, and the configurations were found to be stable during 50 ns simulations. We performed MD simulations of two tubules in proximity to better understand the aggregation of these fibrils and how the fibrils interact in order to stick together. We found that an interfibril network of noncovalent bonds, in particular van der Waals and π-π contacts, which is formed between the ferulic acid groups of oryzanol through the hydroxyl, methoxy, and aromatic groups, is responsible for the surface-to-surface interactions between fibrils; an observation supported by molecular spectroscopy. We believe that these interactions are of primary importance in creating a strong organogel network.

Stable emulsions of droplets in a solid edible organogel matrix.

Sitosterol and oryzanol self-assemble to form very firm gels in a range of organic solvents. However, due to the formation of sitosterol hydrate crystals, these gels are unstable in the presence of water, prohibiting the dispersal of water droplets throughout the gel matrix. We demonstrate that by using glycerol as the polar phase rather than water, droplets may be dispersed throughout the oil phase without disrupting the self-assembly of the gel. As increasing volumes of water are added to the glycerol, the G' values decrease. This can be correlated to both a drop in water activity, and also the stability of the fibrils in the presence of glycerol compared to water, as elucidated by molecular dynamics simulations. We explore how changing the total volume of polar droplets, and changing the water content of these droplets alters the strength of 15% w/w sterol gels. We find that gels exhibit G' values of ∼1 × 107 Pa even with ∼30% w/w glycerol dispersed throughout the matrix. At higher glycerol loadings, complex multiple emulsion morphologies can form.

The development of phytosterol-lecithin mixed micelles and organogels.

We demonstrate that by mixing the phytosterol-ester oryzanol with lecithin in an organic solvent, both components may be dispersed at much higher concentrations than they may be individually. Dynamic light scattering and molecular dynamics simulations show that the mechanism for this is the formation of r ∼ 4 nm mixed micelles. Infrared spectroscopy and simulations suggest that these micelles are formed due in part to hydrogen bonding of the phosphate of the lecithin head-group, and the phenol group of the oryzanol. Rheology shows that by mixing these materials at an equimolar ratio, highly viscous suspensions are created. Furthermore, by adding water to these samples, a solid-like gel may be formed which offers mechanical properties close to those desired for a margarine type spread, whilst still solubilizing the oryzanol.

Microstructure of ß-Sitosterol:γ-Oryzanol Edible Organogels.

Rheology and atomic force microscopy (AFM) were employed to examine the microstructure of ß-sitosterol:γ-oryzanol organogels in sunflower oil. Using time-resolved rheology, we followed gel formation, paying specific attention to the fibril aggregation process, which had not been studied in detail previously for this system. Using AFM, we observed gel structures directly and obtained detailed information on the gel structure, far exceeding previous studies. Our analysis suggests that though gels are formed by the self-assembly and aggregation of one-dimensional fibrils, the manner in which these fibrils aggregate into ribbons results in complex structures of higher dimensionality. We emphasize that it is a surprise to find ribbons and not twisted strands. Comparing AFM images of 10% w/w and 20% w/w gelator systems, we observed differences in the degree of branching which are consistent with the rheology. We also observed the individual self-assembled fibrils which make up these gels with much greater clarity than in previous microscopy studies, and the fibril diameters of ∼9.8 nm we measured agree excellently with those obtained from existing small-angle neutron scattering data. These results provide new insight into the structure and formation kinetics of this important organogel system.

Binding of Caffeine and Quinine by Whey Protein and the Effect on Bitterness.

Many drugs and phytochemicals are bitter, leading to noncompliance with prescriptions and avoidance of healthy foods and a need to suppress their taste. The goal of this study was to investigate the binding of bitterants (quinine and caffeine) by whey protein isolate (WPI) and the effect on perceived bitterness. Caffeine interacted minimally with WPI, while the proportion of unbound quinine decreased exponentially with protein concentration. Molecular modeling was used to show the energy of the quinine-Β-lactoglubulin interaction was an order of magnitude greater than the caffeine-Β-lactoglobulin interaction. Untrained assessors were used to assess the bitterness of caffeine (1.8, 5.7, and 18 mM) and quinine (0.056, 0.10, and 0.18 mM) solutions with 0% or 1% WPI. There was no significant effect of protein on the bitterness of caffeine solutions, but WPI decreased the bitterness of quinine relative to the same concentration in water. This is generally consistent with our hypothesis that higher binding results in lower bitterness; however the magnitude of reduction was not large and the bitterness of the protein-quinine solutions was greater than would be expected for the unbound quinine present.

Effect of addition of thermally modified cowpea protein on sensory acceptability and textural properties of wheat bread and sponge cake.

This paper investigates the sensory acceptability and textural properties of leavened wheat bread and sponge cake fortified with cow protein isolates that had been denatured and glycated by thermal treatment. Defatted cowpea flour was prepared from cow pea beans and the protein isolate was prepared (CPI) and thermally denatured (DCPI). To prepare glycated cowpea protein isolate (GCPI) the cowpea flour slurry was heat treated before isolation of the protein. CPI was more susceptible to thermal denaturation than GCPI as determined by turbidity and sulphydryl groups resulting in greater loss of solubility. This is attributed to the higher glycation degree and higher carbohydrate content of GCPI as demonstrated by glycoprotein staining of SDS PAGE gels. Water absorption of bread dough was significantly enhanced by DCPI and to a larger extent GCPI compared to the control, resulting in softer texture. CPI resulted in significantly increased crumb hardness in baked bread than the control whereas DCPI or GCPI resulted in significantly softer crumb. Bread fortified with 4% DCPI or GCPI was similar to control as regards sensory and textural properties whereas 4% CPI was significantly different, limiting its inclusion level to 2%. There was a trend for higher sensory acceptability scores for GCPI containing bread compared DCPI. Whole egg was replaced by 20% by GCPI (3.5%) in sponge cake without affecting the sensory acceptability, whereas CPI and DCPI supplemented cakes were significantly different than the control.