Alkanes lipids

Alkanals, secondary oxidation products, 665 n-Alkanals, lipid peroxidation, 614 Alkanes... 

Lipid alkoxy radicals (LO ) decompose in chain scission reaction to a great variety of reactive aldehydes such as malonaldehyde, hydroxyalkenals, 2-alkenals, 2,4-alkadienals and alkanals. Lipid alkoxy radicals also cause the degradation of the apolipoprotein B (apoB) to smaller peptide fragments. 

Sophorolipid is a glycolipid, ie it is composed of carbohydrate and lipid. It therefore contains moieties of widely different oxidation levels and its synthesis from single demand carbon sources has a high ATP demand. However, the demand for ATP is reduced if a mixture of glucose and C-18 alkane is used. If glucose and fatty add is used the ATP demand is reduced further and relatively high spedfic production rates can be achieved. 

The SUM was covered by a polymer film with an orifice of approximately 0.3 mm in diameter on each side, and subsequently a folded BLM was generated from a DPhPC/l,2-dipalmitoyl-in-glycero-3-phosphatidic acid (DPPA) monolayer on the side facing the SUM (Fig. 19). Interestingly, no pretreating of the orifice with any alkane or lipid was required, as is imperative for all other BLM techniques. Thus, an accumulation of such compounds could be excluded, and the physicochemical properties of the membrane and... 

Suzuki T, K Tanaka, I Matsubara, S Kinoshita (1969) Trehalose lipid and alpha-branched-beta-hydroxy fatty acid formed by bacteria grown on -alkanes. Agric Biol Chem 33 1619-1627. 

C2-C4 w-alkanes [42,43], and in supercritical carbon dioxide when employing novel surfactants with fluorocarbon tails [38,44], There is also interest in the further employment of lipids (triglycerides and wax esters, such as isopropyl myristate) as solvent to improve biocompatibility [45],... 

D. Small, The Physical Chemistry of Lipids—from Alkanes to Phopholipids, Plenum Press, New York, 1986. 

It is also quite interesting that lipid model 4.0 may be used to obtain alkane partition coefficients at high-throughput speeds, as suggested by Faller and Wohnsland [509,554], It is also interesting to note that since our Pe are corrected for membrane retention, the slope in Fig. 7.11 corresponding to the dashed line (our data) is 1.0, whereas the data not corrected for retention (solid line) show a lesser slope. This may not matter if the objective is to obtain alkane-water log Kp values at high speeds. 

Figures 7.31a-c clearly show that after some critical soy content in dodecane, Pe values decrease with increasing soy, for both sink and sinkless conditions. [This is not due to a neglect of membrane retention, as partly may be the case in Fig. 7.23 permeabilities here have been calculated with Eq. (7.21).] Section 7.6 discusses the Kubinyi bilinear model (Fig. 7.19d) in terms of a three-compartment system water, oil of moderate lipophilicity, and oil of high lipophilicity. Since lipo-some(phospholipid)-water partition coefficients (Chapter 5) are generally higher than alkane-water partition coefficients (Chapter 4) for drug-like molecules, soy lecithin may be assumed to be more lipophilic than dodecane. It appears that the increase in soy concentration in dodecane can be treated by the Kubinyi analysis. In the original analysis [23], two different lipid phases are selected at a fixed ratio (e.g., Fig. 7.20), and different molecules are picked over a range of lipophilicities.

Seiler [250] proposed a way of estimating the extent of hydrogen bonding in solute partitioning between water and a lipid phase by measuring the so-called A log P parameter. The latter parameter is usually defined as the difference between the partition coefficient of a solute measured in the octanol-water system and that measured in an inert alkane-water suspension AlogP = log Kp oet — log Kp aik. 

Results of parameter optimization and MD simulations of small model compounds have been published, including alcohols [63], alkanes [63], aromatic [64] and heteroaromatic [209] compounds and liquid amides [65], Studies of ions in aqueous solution were also performed [61, 88] and results from an MD simulation on a DPPC lipid monolayer have been reported (Harder, MacKerell, Roux, submitted). Notable from the monolayer study was the reproduction of the dipole potential across the monolayer, a value that cannot be reproduced using non-polarizable models. This exciting, unforeseen observation points to the types of results that may be obtained from polarizable macromolecular force fields that are not accessible to the present additive models. 

The formation of lipid components in an aqueous phase at temperatures from 370 to 620 K was studied by Rushdie and Simoneit (2001), who heated aqueous solutions of oxalic acid in a steel vessel for 2 days the yield of oxidized compounds reached a maximum (5.5% based on oxalic acid) between 420 and 520 K. A broad spectrum of compounds was obtained, from n-alkanes to the corresponding alcohols, aldehydes and ketones. At higher temperatures, i.e., above 520-570 K, cracking reactions competed with the synthetic reactions. 

Mueller et al. [6] discovered in 1962 that when a small quantity of a phospholipid (2% wt/vol alkane solution) was carefully placed over a small hole (0.5 mm) in a thin sheet of Teflon or polyethylene (10-25 pm thick), a thin film gradually forms at the center of the hole, with excess lipid flowing towards the perimeter (forming a Plateau-Gibbs border ). Eventually, the central film turns optically black as a single (5 nm-thick) bilayer lipid membrane (BLM) forms over the hole. Suitable lipids for the formation of a BLM are mostly isolated from natural sources, e.g.,... 

This test is used for both in vitro and in vivo determinations. It involves reacting thiobarbituric acid (TBA) with malondialdehyde (MDA), produced by lipid hydroperoxide decomposition, to form a red chromophore with peak absorbance at 532 nm (Fig. 10.1). The TBARS reaction is not specific. Many other substances, including other alkanals, proteins, sucrose, or urea, may react with TBA to form colored species that can interfere with this assay. 

Molecular fossils have been successfully identified in younger Precambrian rocks and linked to certain classes of biological source material. In organic analyses of ancient sediments the cleaned, pulverized rocks are treated with organic solvents to extract a soluble fraction containing the less complex and more easily identifiable compounds. However, this fraction is more subject to contamination since it is not locked within the rock matrix. Normal alkanes have been identified in extracts of the 3 billion year old Fig Tree Shale. These alkanes have a probable biological origin in cellular lipids. The odd and even-numbered alkanes are evenly distributed, a characteristic of alkanes from ancient rocks. It is uncertain, however, whether these compounds were present at the time of deposition or derived from a later source [24]. 

As well as fluorescence-based assays, artificial membranes on the surface of biosensors offered new tools for the study of lipopeptides. In a commercial BIA-core system [231] a hydrophobic SPR sensor with an alkane thiol surface was incubated with vesicles of defined size distribution generating a hybrid membrane by fusion of the lipid vesicles with the alkane thiol layer [232]. If the vesicles contain biotinylated lipopeptides their membrane anchoring can be analyzed by incubation with streptavidine. Accordingly, experiments with lipopeptides representing the C-terminal sequence of N-Ras show clear differences between single and double hydrophobic modified peptides in their ability to persist in the lipid layer [233]. 

The results summarized above were obtained by using fluorescence based assays employing phospholipid vesicles and fluorescent labeled lipopeptides. Recently, surface plasmon resonance (SPR) was developed as new a technique for the study of membrane association of lipidated peptides. Thus, artificial membranes on the surface of biosensors offered new tools for the study of lipopeptides. In SPR (surface plasmon resonance) systemsI713bl changes of the refractive index (RI) in the proximity of the sensor layer are monitored. In a commercial BIAcore system1341 the resonance signal is proportional to the mass of macromolecules bound to the membrane and allows analysis with a time resolution of seconds. Vesicles of defined size distribution were prepared from mixtures of lipids and biotinylated lipopeptides by extruder technique and fused with a alkane thiol surface of a hydrophobic SPR sensor. 

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