Physicochemical Properties Of Lipids Research Articles

Lipid Peroxidation Drives Liquid-Liquid Phase Separation and Disrupts Raft Protein Partitioning in Biological Membranes.

The peroxidation of membrane lipids by free radicals contributes to aging, numerous diseases, and ferroptosis, an iron-dependent form of cell death. Peroxidation changes the structure and physicochemical properties of lipids, leading to bilayer thinning, altered fluidity, and increased permeability of membranes in model systems. Whether and how lipid peroxidation impacts the lateral organization of proteins and lipids in biological membranes, however, remains poorly understood. Here, we employ cell-derived giant plasma membrane vesicles (GPMVs) as a model to investigate the impact of lipid peroxidation on ordered membrane domains, often termed membrane rafts. We show that lipid peroxidation induced by the Fenton reaction dramatically enhances the phase separation propensity of GPMVs into coexisting liquid-ordered (Lo) and liquid-disordered (Ld) domains and increases the relative abundance of the disordered phase. Peroxidation also leads to preferential accumulation of peroxidized lipids and 4-hydroxynonenal (4-HNE) adducts in the disordered phase, decreased lipid packing in both Lo and Ld domains, and translocation of multiple classes of raft proteins out of ordered domains. These findings indicate that the peroxidation of plasma membrane lipids disturbs many aspects of membrane rafts, including their stability, abundance, packing, and protein and lipid composition. We propose that these disruptions contribute to the pathological consequences of lipid peroxidation during aging and disease and thus serve as potential targets for therapeutic intervention.

Inhibitory Efficiency and Physicochemical Properties of Lipids from Leaves and Juice of Aloe arborescens Mill.

Inhibitory Efficiency and Physicochemical Properties of Lipids from Leaves and Juice of Aloe arborescens Mill.

Fluidity is the way to life: lipid phase separation in bacterial membranes.

A hallmark of biological membranes is the dynamic localization of lipids and proteins. Lipids respond to temperature reduction below a critical point with phase separation, and poikilothermic animals and also bacteria adapt their lipid content to prevent gel phase formation in membranes. In a new study, Gohrbandt etal (2022) show that reduced membrane fluidity in bacterial cells causes reversible phase separation without membrane rupture invivo, highlighting the physical robustness of biological membranes.

Membrane hydrophobicity determines the activation free energy of passive lipid transport

The collective behavior of lipids with diverse chemical and physical features determines a membrane’s thermodynamic properties. Yet, the influence of lipid physicochemical properties on lipid dynamics, in particular interbilayer transport, remains underexplored. Here, we systematically investigate how the activation free energy of passive lipid transport depends on lipid chemistry and membrane phase. Through all-atom molecular dynamics simulations of 11 chemically distinct glycerophospholipids, we determine how lipid acyl chain length, unsaturation, and headgroup influence the free energy barriers for two elementary steps of lipid transport: lipid desorption, which is rate limiting, and lipid insertion into a membrane. Consistent with previous experimental measurements, we find that lipids with longer, saturated acyl chains have increased activation free energies compared to lipids with shorter, unsaturated chains. Lipids with different headgroups exhibit a range of activation free energies; however, no clear trend based solely on chemical structure can be identified, mirroring difficulties in the interpretation of previous experimental results. Compared to liquid-crystalline phase membranes, gel phase membranes exhibit substantially increased free energy barriers. Overall, we find that the activation free energy depends on a lipid’s local hydrophobic environment in a membrane and that the free energy barrier for lipid insertion depends on a membrane’s interfacial hydrophobicity. Both of these properties can be altered through changes in lipid acyl chain length, lipid headgroup, and membrane phase. Thus, the rate of lipid transport can be tuned through subtle changes in local membrane composition and order, suggesting an unappreciated role for nanoscale membrane domains in regulating cellular lipid dynamics.

Asymmetric Lipid Transfer between Zwitterionic Vesicles by Nanoviscosity Measurements.

The interest in nano-sized lipid vesicles in nano-biotechnology relies on their use as mimics for endosomes, exosomes, and nanocarriers for drug delivery. The interactions between nanoscale size lipid vesicles and cell membranes involve spontaneous interbilayer lipid transfer by several mechanisms, such as monomer transfer or hemifusion. Experimental approaches toward monitoring lipid transfer between nanoscale-sized vesicles typically consist of transfer assays by fluorescence microscopy requiring the use of labels or calorimetric measurements, which in turn require a large amount of sample. Here, the capability of a label-free surface-sensitive method, quartz crystal microbalance with dissipation monitoring (QCM-D), was used to monitor lipid transfer kinetics at minimal concentrations and to elucidate how lipid physicochemical properties influence the nature of the transfer mechanism and dictate its dynamics. By studying time-dependent phase transitions obtained from nanoviscosity measurements, the transfer rates (unidirectional or bidirectional) between two vesicle populations consisting of lipids with the same head group and differing alkyl chain length can be estimated. Lipid transfer is asymmetric and unidirectional from shorter-chain lipid donor vesicles to longer-chain lipid acceptor vesicles. The transfer is dramatically reduced when the vesicle populations are incubated at temperatures below the melting of one of the vesicle populations.

Limits of temperature adaptation and thermopreferendum

BackgroundManaging the limits of temperature adaptation is relevant both in medicine and in biotechnology. There are numerous scattered publications on the identification of the temperature limits of existence for various organisms and using different methods. Dmitry Petrovich Kharakoz gave a general explanation for many of these experimental results. The hypothesis implied that each cycle of synaptic exocytosis includes reversible phase transitions of lipids of the presynaptic membrane due to the entry and subsequent removal of calcium ions from the synaptic terminal. The correspondence of the times of phase transitions has previously been experimentally shown on isolated lipids in vitro. In order to test the hypothesis of D.P. Kharakoz in vivo, we investigated the influence of the temperature of long-term acclimatization on the temperature of heat and cold shock, as well as on the kinetics of temperature adaptation in zebrafish. Testing the hypothesis included a comparison of our experimental results with the results of other authors obtained on various models from invertebrates to humans.ResultsThe viability polygon for Danio rerio was determined by the minimum temperature of cold shock (about 6 °C), maximum temperature of heat shock (about 43 °C), and thermopreferendum temperature (about 27 °C). The ratio of the temperature range of cold shock to the temperature range of heat shock was about 1.3. These parameters obtained for Danio rerio describe with good accuracy those for the planarian Girardia tigrina, the ground squirrel Sermophilus undulatus, and for Homo sapiens.ConclusionsThe experimental values of the temperatures of cold shock and heat shock and the temperature of the thermal preferendum correspond to the temperatures of phase transitions of the lipid-protein composition of the synaptic membrane between the liquid and solid states. The viability range for zebrafish coincides with the temperature range, over which enzymes function effectively and also coincides with the viability polygons for the vast majority of organisms. The boundaries of the viability polygon are characteristic biological constants. The viability polygon of a particular organism is determined not only by the genome, but also by the physicochemical properties of lipids that make up the membrane structures of synaptic endings. The limits of temperature adaptation of any biological species are determined by the temperature range of the functioning of its nervous system.

New perspective toward nutritional support for malnourished cancer patients: Role of lipids.

To improve the difficulties related to malnutrition, nutritional support has become an essential part of multidisciplinary comprehensive treatment for cancer. Lipids are essential nutrient source for the human body, and nowadays in clinical practices, it has a positive interventional effect on patients suffering from cancer. However, contribution of lipids in nutritional support of cancer patients is still poorly understood. Moreover, the sensory and physicochemical properties of lipids can severely restrict their applications in lipid-rich formula foods. In this review article, for the first time, we have presented a summary of the existing studies which were related to the associations between different lipids and improved malnutrition in cancer patients and discussed possible mechanisms. Subsequently, we discussed the challenges and effective solutions during processing of lipids into formula foods. Further, by considering existing problems in current lipid nutritional support, we proposed a novel method for the treatment of malnutrition, including developing individualized lipid nutrition for different patients depending on the individual's genotype and enterotype. Nonetheless, this review study provides a new direction for future research on nutritional support and the development of lipid-rich formula foods for cancer patients, and probably will help to improve the efficacy of lipids in the treatment of cancer malnutrition.

Lipids for Taste masking and Taste assessment in pharmaceutical formulations

Pharmaceutical products often have drawbacks of unacceptable taste and palatability which makes it quite difficult for oral administration to some special populations like pediatrics and geriatrics. To curb this issue different approaches like coating, granulation, extrusion, inclusion complexation, ion-exchange resins, etc for taste masking are employed and among them use of lipids have drawn special attention of researchers. Lipids have a lower melting point which is ideal for incorporating drugs in some of these methods like hot-melt extrusion, melt granulation, spray drying/congealing and emulsification. Lipids play a significant role as a barrier to sustain the release of drugs and biocompatible nature of lipids increases their acceptability by the human body. Further, lipids provide vast opportunities of altering pharmacokinetics of the active ingredients by modulating release profiles. In taste sensors, also known as electronic tongue or e-tongue, lipids are used in preparing taste sensing membranes which are subsequently used in preparing taste sensors. Lipid membrane taste sensors have been widely used in assessing taste and palatability of pharmaceutical and food formulations. This review explores applications of lipids in masking the bitter taste in pharmaceutical formulations and significant role of lipids in evaluation of taste and palatability.

The Utility of Lipids as Nanocarriers and Suitable Vehicle in Pharmaceutical Drug Delivery

Lipid based excipients have gained popularity recently in the formulation of drugs in order to improve their pharmacokinetic profiles. For drugs belonging to the Biopharmaceutics Classification System (BCS) class II and IV, lipid excipients play vital roles in improving their pharmacokinetics properties. Various nanocarriers viz: Solid lipid nanoparticles, nanostructured lipid carriers, selfnanoemulsifying drug delivery systems (SNEDDS), nanoliposomes and liquid crystal nanoparticles have been employed as delivery systems for such drugs with evident successes. Lipid-based nanotechnology have been used to control the release of drugs and have utility for drug targeting and hence, have been used for the delivery of various anticancer drugs and for colon targeting. Drugs encapsulated in lipids have enhanced stability due to the protection they enjoy in the lipid core of these nanoformulations. However, lipid excipients could be influenced by factors which could affect the physicochemical properties of lipid-based drug delivery systems (LBDDS). These factors include the liquid crystalline phase transition, lipid crystallization and polymorphism amongst others. However, some of the physicochemical properties of lipids made them useful as nanocarriers in the formulation of various nanoformulations. Lipids form vesicles of bilayer which have been used to deliver drugs and are often referred to as liposomes and nanoliposomes. This work aims at reviewing the different classes of lipid excipients used in formulating LBDDS and nanoformulations. Also, some factors that influence the properties of lipids, different polymorphic forms in lipid excipients that made them effective nanocarriers in nano-drug delivery would be discussed. Special considerations in selecting lipid excipients used in formulating various forms of nanoformulations would be discussed.

Rational selection of reverse phase columns for high throughput LC-MS lipidomics.

Natural lipidomes are characterized by extremely high complexity and dynamic range of lipid concentrations. Furthermore, high diversity of lipid physicochemical properties requires high resolving powers for both chromatographic and mass spectrometric analytical platforms. Reverse-phase chromatography coupled with data-dependent MS/MS acquisition is one of the most popular techniques in untargeted lipidomics. Optimal method should provide good chromatographic separation and resolution, reproducibility, selectivity and sensitivity. Here, we developed and set-up a RPLC-MS/MS workflow capable of resolving complex mixtures of lipids in 32 min of analysis. Human blood plasma was chosen as a representative complex natural lipidome with large variance of lipid classes, species and lipid concentrations. Lipids were separated by RPLC on five different reverse phase columns with different types of stationary phase particles, size and chemistry. High mass accuracy MS analysis and data-dependent MS/MS analysis were performed using a Q Exactive™ HF Hybrid Quadrupole-Orbitrap™ Mass Spectrometer to identify individual lipid molecular species. This workflow was applied to evaluate the separation capability of each column and to identify the lipidomics profile in highly complex biological samples. As a result, we report more than 600 lipid species covering 18 lipid classes in human blood plasma and provide suggestions to the selection of the appropriate reverse phase column for the analysis of specific lipidomes.

산림자원에서 추출한 유지자원의 영양성분 및 이화학적 특성 검토

본 연구에서는 산림자원에서 추출한 유지자원의 이용에 대한 잠재력을 확인하고자 지용성 영양성분에 대한 연구와 이를 토대로 한 이화학적 특성을 확인해 보았다. 영양성분의 경우 높은 불포화 지방의 비율(80%)을 보였고, 지용성 비타민인 tocopherols과 식물성 스테롤인 phytosterol의 다양한 함량 분포를 확인하였다. 이화학적인 특성을 볼 때 1차 산화생성물인 산가와 과산화물가의 값은 안정적인 값이었으며, 2차 산화생성물의 지표인 p-anisidine value의 값을 확인하였다. 갈변도와 색도의 경우 유지 자체의 색도를 포함한 값으로 인해 신선도를 판정하기에는 무리가 있으나 색도에 대한 정보를 통해 적용 분야를 적용할 수 있는 근거로써 이용이 가능할 것으로 보인다. 산화안정성의 지표인 산소유도기간에서도 불포화지방산과 지용성 항산화제인 α-T의 함량에 따른 다양한 결과를 보였다. 본 연구는 영양성분 및 이화학적인 결과를 산림유지 자원의 이용을 위한 기초자료로서 활용이 가능다고 판단된다.

Design of lipid microparticle dispersions based on the physicochemical properties of the lipid and aqueous phase

Lipid microparticle (LMP) dispersions may be utilized as novel pharmaceutical dosage forms for different administration routes. The particle size and particle size distribution of the LMPs can be classified to the most crucial specifications for therapeutical and research applications. The size parameters can be adjusted via the physicochemical properties of the inner lipid and the outer aqueous phase. In the present study, ten different solid lipids with incorporated lecithin and four concentrations of the surfactant poloxamer 407 (P407) were utilized for LMP dispersion preparation. Physicochemical properties of the bulk and dispersed lipid matrices as well as features of the P407 solutions were determined. Correlations between the mean particle size (mean) of the LMPs and the span as parameter for the particle size distribution as responses were identified by plotting against the measured physicochemical parameters. Most significant linear correlations were found between the mean and the micellization onset temperature (Tmicell) in the parent solution and the dynamic viscosity of the emulsifier solution at 25°C and between the span and the Tmicell in the LMP dispersion. Consequently, P407 micelles as a reservoir for surfactant monomers and the overall viscosity as a separator between newly-formed lipid droplets are fundamental stabilizing parameters.

Optimization and characterization of biodiesel production from microalgae Botryococcus grown at semi-continuous system

The indigenous strain Botryococcus braunii TN101 was isolated and acclimatized under laboratory condition. Upstream and downstream process was thoroughly explored for biofuel production. During semi-continuous cultivation, the alga was grown under batch mode for 6days; thereafter 40% of algal culture was harvested at every three days interval. At semi-continuous system, the indigenous strain grows well and produces high biomass productivity of 33.8gm−3day−1. A two step combined harvesting process was designed using ferric iron and organic polymer Poly-(d)glucosamine and harvested 99.5% of biomass. Lipid extraction was optimized using different solvents, cyclohexane and methanol at 3:1 ratio supported for maximum extraction of lipids in Botryococcus up to 26.3%. Physicochemical properties of lipid was analyzed and found, saponification values 184, ester values 164, iodine values 92 and the average molecular weight of the lipids are 920gmol−1. The lipid contains 9.7% of FFA level, therefore, a simultaneous esterification and transesterification of free fatty acids and triacylglycerides were optimized for biodiesel production and the methyl ester yield was recorded up to 84%. In addition, an optimization study was carried out for the removal of pigments present in the biodiesel; the result revealed that 99% of pigments were removed from the biodiesel using activated charcoal. The biodiesel profile was analyzed by 1H and 13C NMR and GC–MS analyzer, methyl palmitate and methyl oleate was the major fatty acid found. Based on the areal and volumetric biomass productivity, it is estimated that the indigenous strain can produce 101tonsha−1year−1 of biomass.

Lamellar Gel (Lβ) Phases of Ternary Lipid Composition Containing Ceramide and Cholesterol

Lipid lateral segregation into specific domains in cellular membranes is associated with cell signaling and metabolic regulation. This phenomenon partially arises as a consequence of the very distinct bilayer-associated lipid physico-chemical properties that give rise to defined phase states at a given temperature. Until now lamellar gel (Lβ) phases have been described in detail in single or two-lipid systems. Using x-ray scattering, differential scanning calorimetry, confocal fluorescence microscopy, and atomic force microscopy, we have characterized phases of ternary lipid compositions in the presence of saturated phospholipids, cholesterol, and palmitoyl ceramide mixtures. These phases stabilized by direct cholesterol-ceramide interaction can exist either with palmitoyl sphingomyelin or with dipalmitoyl phosphatidylcholine and present intermediate properties between raft-associated phospholipid-cholesterol liquid-ordered and phospholipid-ceramide Lβ phases. The present data provide novel, to our knowledge, evidence of a chemically defined, multicomponent lipid system that could cooperate in building heterogeneous segregated platforms in cell membranes.

The Chemical Nature of the Polar Functional Group of Oxidized Acyl Chain Uniquely Modifies the Physicochemical Properties of Oxidized Phospholipid-Containing Lipid Particles

Oxidative modification of phospholipids generates a variety of oxidized phospholipid (Ox-PL) species which differ considerably in their chemical compositions and molecular structures. Recent results suggest that even closely related Ox-PL species can have considerably different biological effects. However, the molecular mechanism for this is not yet clear. In truncated Ox-PLs (tOx-PLs) the fatty acyl chain is shorter in length than the parent nonoxidized phospholipid molecules and contains a polar functional group(s). In a previous study we showed that two closely related tOx-PL species having a similar polar functional group and differing only in the length of the oxidized fatty acyl chain exerts significantly different effects on the physicochemical properties of the nonoxidized phospholipid particles containing these lipids (Kar et al., Chem Phys Lipids 164:54-61, 2011). In this study we have characterized the effect of polar functional groups of oxidized fatty acyl chain on the physicochemical properties of the nonoxidized phospholipid particles containing these lipids. Our results show that Ox-PL species differing only in the chemical nature of polar functional groups in their oxidized fatty acyl chain modify the properties of nonoxidized phospholipid particles containing them in a distinctive way. These results indicate that different species of Ox-PLs induce unique changes in the physicochemical properties of lipid particles/membranes containing them and that this may lead to their different biological effects.

Interrelation between structural state, physicochemical properties and lipid composition in microbial cells

We performed complex investigations of antioxidant properties and the lipid composition of the five gram-negative bacteria depending on the cultivation season. Structural state, the lipid composition and physicochemical properties of lipids of the three gram-negative bacteria (Renobacter vacuolatum, Flectobacillus major WKM 869, Pseudomonas fluorescens) during their growth and mycelium of four species of the xylotrophic basidiomycetes (Panus tigrinus IBK-131, Fomes fomentarius M71, Laetiporus sulfureus M131, Piptoporus betulinus M60) during the lag phase were also studied. Changes in the composition of the lipid component in the studied bacteria led to considerable structural rearrangements in their membrane system during the growth of bacteria. It is shown that more hydrophilic regions of the lipid component are of paramount importance in maintaining the fluidity of the entire lipid bilayer in the basidiomycete mycelium. The scale and direction of the revealed interrelations between rotational correlation times of probes and the lipid composition depend both on localization of the probe in membrane and the composition and physicochemical properties of the microorganism lipids.

Reversed Phase HPLC Analysis of Stability and Microstructural Effects on Degradation Kinetics of β-Carotene Encapsulated in Freeze-Dried Maltodextrin–Emulsion Systems

Degradation of dispersed lipophilic compounds in hydrophilic solids depends upon matrix stability and lipid physicochemical properties. This study investigated effects of solid microstructure and size of lipid droplets on the stability of dispersed β-carotene in freeze-dried systems. Emulsions of β-carotene in sunflower oil were dispersed in maltodextrin systems (M040/DE6, M100/DE11, and M250/DE25.5) (8% w/w oil) and prefrozen at various freezing conditions prior to freeze-drying to control nucleation and subsequent pore size and structural collapse of freeze-dried solids. The particle size, physical state, and β-carotene contents of freeze-dried emulsions were measured during storage at various water activity (a(w)) using a laser particle size analyzer, differential scanning calorimeter, and high performance liquid chromatography (HPLC), respectively. The results showed that M040 stabilized emulsions in low temperature freezing exhibited lipid crystallization. Collapse of solids in storage at a(w) which plasticized systems to the rubbery state led to flow and increased the size of oil droplets. Degradation of β-carotene analyzed using a reversed-phase C(30) column followed first-order kinetics. Porosity of solids had a major effect on β-carotene stability; however, the highest stability was found in fully plasticized and collapsed solids.

Violaxanthin and diadinoxanthin cycles as an important photoprotective mechanism in photosynthesis

The molecular mechanism and regulation of violaxanthin (Vx) and diadinoxanthin (Ddx) cycle are discussed. The influence of lipids on the de-epoxidation of the xanthophyll cycle pigments was investigated. Experiments on the significance of physical properties of the aggregates formed by inverted lipid micelles, which are necessary for de-epoxidation, on the conversion of Vx into antheraxanthin (Ax) and zeaxanthin (Zx) and diadinoxanthin (Ddx) to diatoxanthin (Dtx) were performed. Thickness of the hydrophobic fraction of the aggregates, size of the inverted micelles, suggested by mathematical description of the structures, and solubility of Vx and Ddx in various kinds of lipids were the next tested parameters. Obtained results show that the rate of de-epoxidation was strongly dependent on physicochemical properties of lipids. The key role for enzyme activation play non-bilayer lipids and the parameters of inverted micelles created by them, such as thickness, molecular dynamics of hydrophobic core, and their diameter. Additionally the influence of thylakoid lipids on the de-epoxidation of Vx, associated with the light-harvesting complex of PSII (LHCII) were carried out. Almost complete Vx de-epoxidation in the LHCII fractions containing high amounts of endogenous monogalactosyldiacylglycerol (MGDG) was observed in in vitro assays. LHCII preparations with low concentrations of MGDG exhibited a strongly reduced Vx de-epoxidation, which could be increased by addition of exogenous, pure MGDG. The presented results showed that MGDG and other nonlamellar lipids are necessary for the solubilization of Vx and Ddx and they provide also the three-dimensional structures, which are needed for the binding of de-epoxidases and for the accessibility of Vx and Ddx to these enzymes.

Replication of simulated prebiotic amphiphile vesicles controlled by experimental lipid physicochemical properties

We present a new embodiment of the graded autocatalysis replication domain (GARD) for the growth, replication and evolution of lipid vesicles based on a semi-empirical foundation using experimentally measured kinetic values of selected extant lipid species. Extensive simulations using this formalism elucidated the details of the dependence of the replication and properties of the vesicles on the physicochemical properties and concentrations of the lipids, both in the environment and in the vesicle. As expected, the overall concentration and number of amphiphilic components strongly affect average replication time. Furthermore, variations in acyl chain length and unsaturation of vesicles also influence replication rate, as do the relative concentrations of individual lipid types. Understanding of the dependence of replication rates on physicochemical parameters opens a new direction in the study of prebiotic vesicles and lays the groundwork for future studies involving the competition between lipid vesicles for available amphiphilic monomers.

Effect of physicochemical properties of murine liver lipids on the interrelation between the parameters of their composition

The effect of properties of liver lipids on the interrelation between the contents of different lipid fractions has been studied on nine groups of intact SHK female mice. To reveal interrelations, lipids were divided into four groups depending on their antioxidative activity, prooxidant properties, antiperoxide activity, and the content of peroxide in lipids. The data obtained indicate that the physicochemical properties of lipids affect the biosynthesis and degradation of phospholipids, which plays a significant role in the origination of consequences under the action of unfavourable factors on biological objects having the different intensity of oxidative processes.