Sulfolipids

Product-ion mass spectrometric analysis of the deprotonated sulfolipid ions in the negative-ion mode after low-energy CID demonstrates two types of abundant fragment ions  

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Biological exposure pathway of sulfur movement in soils of forest ecosystems is related to microbial transformation of sulfolipids. Back conversion of sulfate-S into organic matter immobilizes the anion and potentially reduces soil cation leaching. Processes of sulfur mineralization and incorporation proceed rapidly in response to several factors, including temperature, moisture, and exogenous sulfate availability in soils and water. 

A more drastic influence of subphase H concentration can be observed for the sulfolipid analog (8) (Figure 7.). At pH values from 2 up to 5,5 (8) forms two condensed phases, whereas at pH 12, where the nitrogen is deprotonated, there is only one phase present (35). This behavior has a considerable influence on the mono-layer polymerization properties of (8), which is discussed later in this chapter. 

Figure 7. Surface pressure area isotherms of sulfolipid (8) at different pHs (35).

The sugar sulfonic acid is l-0-(6-deoxy-6-sulfo-a-D-glucopyranosyl)-glycerol isolated from a plant sulfolipid.46 The plant sulfolipid... 

Chloroplasts also contain the following sulfolipid, an anionic sulfonate. 

Glycolipids are important constituents of the plasma membranes, of the endoplasmic reticulum, and of chloroplasts. The cerebrosides and their sulfate esters, the sulfatides, are especially abundant in myelin. In plant membranes, the predominant lipids are the galactosyl diglycerides.29 74 The previously described ether phospholipids (archaebacteria), ceramide arnino-ethylphosphonate (invertebrates), and sulfolipid (chloroplasts) are also important membrane components. 

Figure 21-3 Major pathways of synthesis of fatty acids and glycerolipids in the green plant Arabidopsis. The major site of fatty acid synthesis is chloroplasts. Most is exported to the cytosol as oleic acid (18 1). After conversion to its coenzyme A derivative it is converted to phosphatidic acid (PA), diacylglycerol (DAG), and the phospholipids phosphatidylcholine (PC), phosphatidylinositol (PI), phosphatidylglycerol (PG), and phosphatidylethanolamine (PE). Desaturation also occurs, and some linoleic and linolenic acids are returned to the chloroplasts. See text also. From Sommerville and Browse.106 See also Figs. 21-4 and 21-5. Other abbreviations monogalactosyldiacylglycerol (MGD), digalactosyldiacylglycerol (DGD), sulfolipid (SL), glycerol 3-phosphate (G3P), lysophosphatidic acid (LPA), acyl carrier protein (ACP), cytidine diphosphate-DAG (CDP-DAG).

Fig. 24-25), another component of nervous tissue. Cysteic acid can arise in an alternative way from O-acetylserine and sulfite (reaction 1, Fig. 24-25), and taurine can also be formed by decarboxylation of cysteine sulfinic acid to hypotaurine and oxidation of the latter (reaction m). Cysteic acid can be converted to the sulfolipid of chloroplasts (p. 387 Eq. 20-12). 

The fact that the polyreaction of diacetylenes is topochemically controlled is especially well documented by the polymerization behavior of the sulfolipid (22)23 . (22) forms two condensed phases when spread on an acidic subphase at elevated temperatures (Fig. 10). UV initiated polymerization can only be carried out at low surface pressures in the first condensed phase, where the molecules are less densely packed. Apparently, in the second phase at surface pressures from 20 to 50 mN/m the packing of the diyne groups is either too tight to permit a topochemical polymerization or a vertical shift of the molecules at the gas/water interface causes a transition from head packing to chain packing (Fig. 10), thus preventing the formation of polymer. 

Whether polymerized model membrane systems are too rigid for showing a phase transition strongly depends on the type of polymerizable lipid used for the preparation of the membrane. Especially in the case of diacetylenic lipids a loss of phase transi tion can be expected due to the formation of the rigid fully conjugated polymer backbone 20) (Scheme 1). This assumption is confirmed by DSC measurements with the diacetylenic sulfolipid (22). Figure 25 illustrates the phase transition behavior of (22) as a function of the polymerization time. The pure monomeric liposomes show a transition temperature of 53 °C, where they turn from the gel state into the liquid-crystalline state 24). During polymerization a decrease in phase transition enthalpy indicates a restricted mobility of the polymerized hydrocarbon core. Moreover, the phase transition eventually disappears after complete polymerization of the monomer 24). 

As an example of an asymmetric membrane integrated protein, the ATP synthetase complex (ATPase from Rhodospirillum Rubrum) was incorporated in liposomes of the polymerizable sulfolipid (22)24). The protein consists of a hydrophobic membrane integrated part (F0) and a water soluble moiety (Ft) carrying the catalytic site of the enzyme. The isolated ATP synthetase complex is almost completely inactive. Activity is substantially increased in the presence of a variety of amphiphiles, such as natural phospholipids and detergents. The presence of a bilayer structure is not a necessary condition for enhanced activity. Using soybean lecithin or diacetylenic sulfolipid (22) the maximal enzymatic activity is obtained at 500 lipid molecules/enzyme molecule. With soybean lecithin, the ATPase activity is increased 8-fold compared to a 5-fold increase in the presence of (22). There is a remarkable difference in ATPase activity depending on the liposome preparation technique (Fig. 41). If ATPase is incorporated in-... 

In addition to enzymatic hydrolysis of natural lipids in polymeric membranes as discussed in chapter 4.2.2., other methods have been applied to trigger the release of vesicle-entrapped compounds as depicted in Fig. 37. Based on the investigations of phase-separated and only partially polymerized mixed liposomes 101, methods to uncork polymeric vesicles have been developed. One specific approach makes use of cleavable lipids such as the cystine derivative (63). From this fluorocarbon lipid mixed liposomes with the polymerizable dienoic acid-containing sulfolipid (58) were prepared in a molar ratio of 1 9 101115>. After polymerization of the matrix forming sulfolipids, stable spherically shaped vesicles are obtained as demonstrated in Fig. 54 by scanning electron microscopy 114>. 

The incorporation of a membrane protein into a polymerizable liposome from (22) was demonstrated by R. Pabst n9). The chromoprotein bacteriorhodopsin — a light-driven proton pump from halophilic bacteria — was incorporated into monomeric sulfolipid liposomes by ultrasonication. The resulting proteoliposomes were poly-... 

The proportion of sulfolipids in the gonads of sea urchins changes during early development of the embryos.283 It has also been found that the sulfolipid from P. depressus exerts a stimulating effect on the respiration of the spermatozoa of the sea urchin.308... 

Ciminiello P, Dell Aversano C, Fattorusso E, Forino M, Magno S, Di Rosa M, Ianaro A, Poletti R (2002) Structure and Stereochemistry of a New Cytotoxic Polychlorinated Sulfolipid from Adriatic Shellfish. J Am Chem Soc 124 13114... 

Our initial studies were carried out on cultures of dissociated cells from brains of one day old mice. Unfortunately these preparations had lower than hoped for activities of certain biochemical parameters of myelination. For example, both the incorporation of 35g0jj into sulfolipids and the activity of the cyclic nucleotide phosphohydrolase attained relatively small activities even at the age (8 to 11 days) of optimum activity in culture (fig. 1 and 2). The dissociated cells from the 1 day old mouse produced parallel developmental patterns of both myelin parameters with peak activities at 8 to 11 days in culture. However cultures prepared from 15 day fetal brains proved to have relatively... 

The culture system used in this study has proven suitable for studying the regulation, especially by hormones, of myelina-tion in vitro. Initial studies (35-36), however, showed no effect of 3, 5, 3 -triiodothyronine (T,) on sulfolipid synthesis by dissociated brain cells grown on medium containing 20% calf... 

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