Esterification of Cellulose with Long Fatty Acid Chain through Mechanochemical Method

Mechanochemical reaction, a green synthetic esterification route was utilized to prepare long-chain cellulose esters from microcrystalline cellulose. The influence of reaction conditions such as reaction temperature and time were elucidated. Only low dosage of oleic acid, 1-butyl-3-metylimidazolium acetate, and p-toluenesulfonyl chloride were required. The success of modification reaction was confirmed by Fourier transforms infrared spectroscopy as a new absorbance peak at 1731 cm−1 was observed, which indicated the formation of carbonyl group (C=O). Solid-state nuclear magnetic resonance was also performed to determine the structural property and degree of substitution (DS) of the cellulose oleate. Based on the results, increasing reaction temperature and reaction time promoted the esterification reaction and DS. DS values of cellulose oleates slightly decreased after 12 h reaction time. Besides, X-ray diffraction analysis showed the broadening of the diffraction peaks and thermal stability decreased after esterification. Hence, the findings suggested that grafting of oleic acid’s aliphatic chain onto the cellulose backbone lowered the crystallinity and thermal stability.

Depth- and temperature-specific fatty acid adaptations in ctenophores from extreme habitats

Animals are known to regulate the composition of their cell membranes to maintain key biophysical properties in response to changes in temperature. For deep-sea marine organisms, high hydrostatic pressure represents an additional, yet much more poorly understood, perturbant of cell membrane structure. Previous studies in fish and marine microbes have reported correlations with temperature and depth of membrane-fluidizing lipid components, such as polyunsaturated fatty acids. Because little has been done to isolate the separate effects of temperature and pressure on the lipid pool, it is still not understood whether these two environmental factors elicit independent or overlapping biochemical adaptive responses. Here, we use the taxonomic and habitat diversity of the phylum Ctenophora to test whether distinct low-temperature and high-pressure signatures can be detected in fatty acid profiles. We measured the fatty acid composition of 105 individual ctenophores, representing twenty-one species, from deep and shallow Arctic, temperate, and tropical sampling locales (sea surface temperature -2° to 28° C). In tropical and temperate regions, remotely operated submersibles (ROVs) enabled sampling down to 4000 meters. Among specimens with body temperatures 7.5°C or colder, depth predicted fatty acid unsaturation level. In the upper 200 m of the water column, temperature predicted fatty acid chain length. Taken together, our findings suggest that lipid metabolism may be specialized with respect to multiple physical variables in diverse marine environments. Largely distinct modes of adaptation to depth and cold imply that polar marine invertebrates may not find a ready refugium from climate change in the deep.

Sunflower and Linseed Oils with Decyl Methacrylate Based Copolymers as Green Lubricating Additives

During the last few years, the greener additives prepared from bio-raw materials with low-cost and multifunctional applications have attracted considerable attention in the field of lubricant industry. In the present work, copolymers derived from sunflower and linseed oils with decyl methacrylate were synthesized by a thermal method using benzoyl peroxide (BPO) as a radical initiator. Direct polymerization through the double bonds of the fatty acid chain in the presence of a free radical initiator leads to the formation of ecofriendly copolymeric additives (P1 and P2). The copolymers were characterized by Fourier Transform Infrared (FTIR) and Proton Nuclear Magnetic Resonance (1H-NMR). Thermal decomposition of copolymers was determined by thermogravimetric analysis. The average molecular weight was measured by gel permeation chromatography (GPC) method. Different concentrations of prepared copolymer as additives vis 1, 2, 3, and 4 (w/v) were used to examine the rheological behavior and performance evaluation of the formulated base oil. The copolymer acts as an excellent viscosity improver and better pour point depressant.

Interaction of cationic antiseptics with cardiolipin-containing model bacterial membranes

Plasma membrane is one of the major targets for cationic antiseptics (CA). The study was aimed to assess molecular effects of CAs of different chemical classes on cardiolipin-containing regions of bacterial plasma membranes. The study was carried out using coarse-grained molecular modeling. Interaction of CAs, such as miramistin, chlorhexidine, picloxidine, and octenidine, with cardiolipin-containing bilayer was assessed based on the CA coarse-grained models. CAs reduced lipid lateral diffusion coefficients and increased the membrane area per lipid. All CAs, except miramistin, reduced the lipid fatty acid chain order parameters. Adding octenidine at a CA : lipid ratio of 1 : 4 resulted in cardiolipin clustering with subsequent pulling the neutral phosphatidylethanolamine molecules out of the model bilayer. It was found that CАs have the potential for sorption to lipid bilayer, causing clustering of negatively charged lipids. Antiseptic octenidine causes formation of cardiolipin microdomains. Abnormal lateral lipid distribution together with pulling out phosphatidylethanolamine molecules can result in increased lipid bilayer permeability. The most significant reduction of cardiolipin lateral diffusion coefficient by 2.8 ± 0.4 times was observed in the presence of CA chlorhexidine at an antiseptic : lipid ratio of 1 : 4.

Molecular-dynamics-simulation-guided membrane engineering allows the increase of membrane fatty acid chain length in Saccharomyces cerevisiae

The use of lignocellulosic-based fermentation media will be a necessary part of the transition to a circular bio-economy. These media contain many inhibitors to microbial growth, including acetic acid. Under industrially relevant conditions, acetic acid enters the cell predominantly through passive diffusion across the plasma membrane. The lipid composition of the membrane determines the rate of uptake of acetic acid, and thicker, more rigid membranes impede passive diffusion. We hypothesized that the elongation of glycerophospholipid fatty acids would lead to thicker and more rigid membranes, reducing the influx of acetic acid. Molecular dynamics simulations were used to predict the changes in membrane properties. Heterologous expression of Arabidopsis thaliana genes fatty acid elongase 1 (FAE1) and glycerol-3-phosphate acyltransferase 5 (GPAT5) increased the average fatty acid chain length. However, this did not lead to a reduction in the net uptake rate of acetic acid. Despite successful strain engineering, the net uptake rate of acetic acid did not decrease. We suggest that changes in the relative abundance of certain membrane lipid headgroups could mitigate the effect of longer fatty acid chains, resulting in a higher net uptake rate of acetic acid.

The Role of Areca catechu Extract on Decreasing Viscosity of Vegetable Oils

The direct use of vegetable oil is constrained by vegetable oils’ viscosity, which is relatively high. Therefore, this study discusses reducing the vegetable oils viscosity molecularly, using natural additives of Areca extract. The role of Areca extract on diminishing the viscosity of vegetable oil was simulated utilizing HyperChem software. Then, the viscosity was verified using the ASTM D445 method. The results show that the epicatechin in the Areca extract generates a local magnetic field on its aromatic ring that plays the role of energizing electron mobility in vegetable oil. On the one hand, increased electron mobility decreases oil polarity but, on the other hand, increases the London force via a temporary dipole charge. Simultaneously, it relaxes oil molecules that tend to increase molecule distance decreasing the London force. Since viscosity is proportional to the London force and oil polarity; thus, these three phenomena determine the role of Areca extract on the oil viscosity. The viscosity reduction is smaller at a larger number of the double bonds in the fatty acid chain since the local magnetic field’s induction on the electron spin is interrupted in the double bonds

Quantitative live-cell PALM reveals nanoscopic Faa4 redistributions and dynamics on lipid droplets during metabolic transitions of yeast

Lipid droplets (LDs) are dynamic organelles for lipid storage and homeostasis. Cells respond to metabolic changes by regulating the spatial distribution of LDs and enzymes required for LD growth and turnover. The small size of LDs precludes the observation of their associated enzyme densities and dynamics with conventional fluorescence microscopy. Here, we employ quantitative photo-activated localization microscopy to study the density of the fatty acid activating enzyme Faa4 on LDs in live yeast cells with single-molecule sensitivity and 30 nm resolution. During the log phase LDs co-localize with the Endoplasmic Reticulum (ER) where their emergence and expansion is mediated by the highest observed Faa4 densities. During transition to the stationary phase LDs with a ∼2-fold increased surface area translocate to the vacuolar surface and lumen and exhibit a ∼2.5-fold increase in Faa4 density. The increased Faa4 density on LDs further suggests its role in LD expansion, is caused by its ∼5-fold increased expression level and is specific to exogenous fatty acid chain-lengths. When lipolysis is induced by refreshed medium, Faa4 shuttles through ER- and lipophagy to the vacuole, where it may activate fatty acids for membrane expansion and degrade to reset cellular Faa4 abundance to levels in the log phase. [Media: see text] [Media: see text] [Media: see text] [Media: see text]

Genetic engineering of the precursor supply pathway for the overproduction of the nC14-surfactin isoform with promising MEOR applications

Background Surfactin, a representative biosurfactant of lipopeptide mainly produced by Bacillus subtilis, consists of a cyclic heptapeptide linked to a β-hydroxy fatty acid chain. The functional activity of surfactin is closely related to the length and isomerism of the fatty acid chain. Results In this study, the fatty acid precursor supply pathway in Bacillus subtilis 168 for surfactin production was strengthened through two steps. Firstly, pathways competing for the precursors were eliminated with inactivation of pps and pks. Secondly, the plant medium-chain acyl-carrier protein (ACP) thioesterase (BTE) from Umbellularia californica was overexpressed. As a result, the surfactin titer after 24 h of cultivation improved by 34%, and the production rate increased from 0.112 to 0.177 g/L/h. The isoforms identified by RP-HPLC and GC–MS showed that the proportion of nC14-surfactin increased 6.4 times compared to the control strain. A comparison of further properties revealed that the product with more nC14-surfactin had higher surface activity and better performance in oil-washing. Finally, the product with more nC14-surfactin isoform had a higher hydrocarbon-emulsification index, and it increased the water-wettability of the oil-saturated silicate surface. Conclusion The obtained results identified that enhancing the supply of fatty acid precursor is very essential for the synthesis of surfactin. At the same time, this study also proved that thioesterase BTE can promote the production of nC14-surfactin and experimentally demonstrated its higher surface activity and better performance in oil-washing. These results are of great significance for the MEOR application of surfactin. Graphic abstract