Edible oleogels as solid fat alternatives: Composition and oleogelation mechanism implications.

The growing awareness of the adverse health effects of trans-fats and saturated fats are driving researchers to seek healthy alternatives. A promising strategy to structure liquid oil, called oleogelation, has been a subject of great interest. In the development of oleogels, highly unsaturated oils can be structured through different gelation mechanisms by varying structuring agents (e.g., polymeric or low molecular weight oleogelators). Due to their potential to reduce saturated fat in food products while also providing solid texture without changing the oil's chemical composition and nutritional values, oleogels have been introduced into various products (meat, spread, and confectionary) as alternatives to traditional solid fats. However, the shortcomings of oleogels cannot be ignored, such as the softer texture and the poorer plasticity than traditional solid fat. As the physicochemical properties and functionalities of oleogels are highly dependent on their composition and structuring mechanism, it is possible to obtain a product with desirable functionality by choosing a suitable oleogelator or oil phase. Thus, comprehensive and detailed knowledge regarding the role of oleoglarors, oil phase, and oleogelation mechanism on oleogelation is needed. This review primarily focuses on published information within the last decades addressing how the composition and oleogelation mechanism affect the structure and functionality of oleogels and oleogel-based products. The factors affecting the oil gelation are summarized concerning three aspects: (i) oleogelator (chemical composition and molecular structure); (ii) oil phase (TAG composition and minor component); and (iii) oleogelation mechanism. Finally, the future perspectives toward oleogels are highlighted. This review aims to deepen the understanding of oleogelation and the rational design of oleogel-based products.

Genetic and chemical approaches for surface charge engineering of enzymes and their applicability in biocatalysis: A review.

Surface charge engineering has received considerable interest from the scientific and industrial community in the last few decades. Although it was previously hypothesized that the surface charge-charge interactions were not a fundamental force to determine protein folding and stability, many studies today show that surface charge plays a key role determining protein structure and activity. This review aims to (a) highlight the value of surface charged engineering of proteins to improve enzyme stability and activity in aqueous media and in the presence of ionic liquids (ILs) and organic solvents, (b) describe the existing approaches (genetic engineering or chemical modifications) for surface charged engineering, and (c) demonstrate the applicability of these surface charged enzymes in biocatalysis. The review provides a new foundation for the scientific and research community to exploit the surface engineering of protein concept for the development of new enzymes that are more active and stable in the presence of ILs and organic solvents, thereby offering new opportunities for industrial biocatalysis. Furthermore, this review is a useful tool for researchers to decide the best available technology to improve their enzyme system/process.

Lignin conversion to ß-ketoadipic acid by Pseudomonas putida via metabolic engineering and bioprocess development.

Bioconversion of a heterogeneous mixture of lignin-related aromatic compounds (LRCs) to a single product via microbial biocatalysts is a promising approach to valorize lignin. Here, Pseudomonas putida KT2440 was engineered to convert mixed p-coumaroyl- and coniferyl-type LRCs to ß-ketoadipic acid, a precursor for performance-advantaged polymers. Expression of enzymes mediating aromatic O-demethylation, hydroxylation, and ring-opening steps was tuned, and a global regulator was deleted. ß-ketoadipate titers of 44.5 and 25 grams per liter and productivities of 1.15 and 0.66 grams per liter per hour were achieved from model LRCs and corn stover-derived LRCs, respectively, the latter representing an overall yield of 0.10 grams per gram corn stover-derived lignin. Technoeconomic analysis of the bioprocess and downstream processing predicted a ß-ketoadipate minimum selling price of $2.01 per kilogram, which is cost competitive with fossil carbon-derived adipic acid ($1.10 to 1.80 per kilogram). Overall, this work achieved bioproduction metrics with economic relevance for conversion of lignin-derived streams into a performance-advantaged bioproduct.

Biodegradation of polyethylene and polystyrene: From microbial deterioration to enzyme discovery.

The global production of plastics has continuously been soaring over the last decades due to their extensive use in our daily life and in industries. Although synthetic plastics offer great advantages from packaging to construction and electronics, their low biodegradability induce serious plastic pollution that damage the environment, human health and make irreversible changes in the ecological cycle. In particular, plastics containing only carbon-carbon (C-C) backbone are less susceptible to degradation due to the lack of hydrolysable groups. The representative polyethylene (PE) and polystyrene (PS) account for about 40% of the total plastic production. Various chemical and biological processes with great potential have been developed for plastic recycle and reuse, but biodegradation seems to be the most attractive and eco-friendly method to combat this growing environmental problem. In this review, we first summarize the current advances in PE and PS biodegradation, including isolation of microbes and potential degrading enzymes from different sources. Next, the state-of-the-art techniques used for evaluating and monitoring PE and PS degradation, the scientific toolboxes for enzyme discovery as well as the challenges and strategies for plastic biodegradation are intensively discussed. In return, it inspires a further technological exploration in expanding the diversity of species and enzymes, disclosing the essential pathways and developing new approaches to utilize plastic waste as feedstock for recycling and upcycling.

Superanionic Solvent-Free Liquid Enzymes Exhibit Enhanced Structures and Activities.

The surface of a carboxylate-enriched octuple mutant of Bacillus subtilis lipase A (8M) is chemically anionized to produce core (8M)-shell (cationic polymer surfactants) bionanoconjugates in protein liquid form, which are termed anion-type biofluids. The resultant lipase biofluids exhibit a 2.5-fold increase in hydrolytic activity when compared with analogous lipase biofluids based on anionic polymer surfactants. In addition, the applicability of the anion-type biofluid using Myoglobin (Mb) that is well studied in anion-type solvent-free liquid proteins is evaluated. Although anionization resulted in the complete unfolding of Mb, the active α-helix level is partially recovered in the anion-type biofluids, and the effect is accentuated in the cation-type Mb biofluids. These highly active anion-type solvent-free liquid enzymes exhibit increased thermal stability and provide a new direction in solvent-free liquid protein research.

Synergistic effects of binary ionic liquid-solvent systems on enzymatic esterification of esculin.

This work established a binary ionic liquid-solvent system for effective enzymatic esterification of naturally occurring phenolic glycosides (flavonoids); which could result in a dramatic enhancement of Novozym 435-catalyzed esterification of esculin, demonstrating a great synergetic effect. In essence, [OMIM][BF4]-toluene and [TOMA][Tf2N]-hexane binary systems both served >90 mol% of conversions of esculin after 96 h of reaction at 60 °C. Typically, binary [TOMA][Tf2N]-hexane system enabled Novozym 435 with extremely high catalytic efficiency (kcat/Km = 17.57 × 10-2 (Ms)-1), which was 55-fold higher than that Novozym 435 exhibited in t-butanol solvent (one of the best solvent systems for esterification reactions). It was also found that the superiormatching in property and structure between IL and solvent was the decisive factor for the outperformance of [TOMA][Tf2N]-hexane binary system, in which [TOMA] and hexane facilitate the solubilization of esculin and fatty acids and [Tf2N]- anions and hexane offer protective effects for lipase at elevated temperatures.

Stability of cellulase in ionic liquids: correlations between enzyme activity and COSMO-RS descriptors.

Ionic liquids (ILs) are effective in pretreating cellulose for enhanced enzymatic saccharification, however ILs can inactivate cellulases. To guide the selection of ILs, the activity of cellulase was correlated with COSMO-RS calculations and descriptors of ILs including hydrogen bond (H-bond) basicity/acidity, polarity and ion size. Trends were deduced using an anion-series and a cation-series of ionic liquids in aqueous solutions. The activity in the cation-series was best correlated with the size of varied cations, whereas the activity in the anion-series showed a pronounced correlation to H-bond basicity and polarity of different anions. COSMO-RS was further used to predict the solubility of cellulose in ILs, which was correlated with cellulase activity on IL-pretreated cellulose. The best correlations were found between the enzyme activity in the anion-series ILs and the logarithmic activity coefficients, the H-bond energy, H-bond basicity and polarizability, underlining that the anion plays a crucial role in cellulose dissolution.

Mapping the location of DATEM in multi-phase systems: Synthesis and characterization of spin-label probe analogues.

Electron paramagnetic resonance (EPR) spectroscopy has emerged as a fast, reliable, non-invasive and sensitive method to determine the distribution, localization and reactivity of labelled ingredients in micro-heterogeneous systems. However, the commercially available probe molecules are very limited. In the present work, five new nitroxide [(4-hydroxy-2, 2, 6, 6-tetramethylpiperidin-1-oxyl (TEMPOL)] derivatives (1b-5b) of diacetyl tartaric acid esters of monoglycerides (DATEM) (1a-5a), a widely used food emulsifier, were synthesized under Steglich conditions and characterized by MS (mass-spectrometry), FT-IR (Fourier-transform infrared spectroscopy), EPR, NMR (nuclear magnetic resonance spectroscopy), fluorescence spectroscopy, and DSC (differential scanning calorimetry) analysis. Phase partitioning studies proved that the new spin labels are adequately capable of describing the localizations and partitioning of the corresponding DATEM in multi-phase systems. Findings disclosed in this work will provide new knowledge on ingredient reactivity and localization in multi-phase systems; which is vital to aid the design of more efficient delivery systems for bioactive compounds.

Aspartic-Acid-Based Ampholytic Amphiphiles: Synthesis, Characterization, and pH-Dependent Properties at Air/Water and Oil/Water Interfaces.

A facile and two-step strategy was employed to synthesize a series of novel aspartic-acid-based ampholytic amphiphiles from sustainable and commercially viable substances as starting materials. The molecular structures of the synthetic compounds were well-identified by mass spectrometry and 1H/13C nuclear magnetic resonance analysis, and the physicochemical, pH-dependent foaming, and emulsifying properties were evaluated by the use of multiple techniques, such as Fourier transform infrared spectroscopy, differential scanning calorimetry, Langmuir-Blodgett study, and fluorescence microscopy imaging. As a result of the co-existence of amino and carboxyl groups in the synthetic compounds, the compounds presented varying charges (cationic, ampholytic, and anionic) depending upon the pH of the medium compared to the dissociation constants (p Ka). Compounds with cationic (pH 1.0) and anionic (pH 9.0) forms had significantly higher γ0.1 and critical micelle concentration values than those with ampholytic forms (pH 7.0). sn-1-Lauroyl- sn-3-aspartic acid (compound 3) at neutral and alkaline conditions displayed comparable foaming properties, including foaming, calcium-tolerant, and temperature-resistant abilities, with commercial sulfonate sodium dodecyl sulfate (SDS), and thus might be a promising alternative to SDS, applied in personal care products and detergent formula. sn-1-Palmtoyl- sn-3-aspartic acid (compound 5a) with an ampholytic structure was proven as the most excellent stabilizer for the preparation of oil-in-water emulsions compared to palmityl aspartic acid (compound 5b), commercial food ingredient diacetyltartaric acid esters of mono- and diglycerides, and glyceride monopalmitate at aqueous phase pH 7.0. Thus, it has promising use as a pH-dependent emulsifying agent in various fields.

Enhanced fish oil-in-water emulsions enabled by rapeseed lecithins obtained under different processing conditions.

It is hypothesized that rapeseed lecithins may have different emulsifying and antioxidant properties in delivering fish oil compared to soy lecithin based on previous studies. The results showed that in vitro antioxidant activities of rapeseed lecithins were stronger than those of soy lecithin. Emulsions stabilized by rapeseed based lecithins and DATEM were stable over 3 months at 4 °C, whereas the creaming of emulsions containing soy lecithin started immediately after its preparation. Zeta-potential of rapeseed lecithins was higher than soy lecithin and DATEM, which partially contributed to the emulsion stability. Although the particle sizes of emulsions prepared by rapeseed lecithins increased after 14 days storage, no creaming was observed. Lipid oxidation as indicated by TBARS values suggested that DATEM was the most unfavorable, followed by soy lecithin. It is concluded that rapeseed lecithins are better than soy lecithin and DATEM in terms of emulsion stability and antioxidant capability, respectively.