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1

Phospholipid asymmetry in large unilamellar vesicles induced by transmembrane pH gradients  

Energy Technology Data Exchange (ETDEWEB)

The influence of membrane pH gradients on the transbilayer distribution of some common phospholipids has been investigated. The authors demonstrate that the transbilayer equilibrium of the acidic phospholipids egg phosphatidylglycerol (EPG) and egg phosphatidic acid (EPA) can be manipulated by membrane proton gradients, whereas phosphatidylethanolamine, a zwitterionic phospholipid, remains equally distributed between the inner and outer monolayers of large unilamellar vesicles (LUVs). Asymmetry of EPG is examined in detail and demonstrated by employing three independent techniques: ion-exchange chromatography, {sup 13}C NMR, and periodic acid oxidation of the (exterior) EPG headgroup. In the absence of a transmembrane pH gradient ({Delta}pH) EPG is equally distributed between the outer and inner monolayers of LuVs. When vesicles composed of either egg phosphatidylcholine (EPC) or DOPC together with 5 mol % EPG are prepared with a transmembrane ...

1989-05-16

2

Interaction of antimicrobial peptides with lipid membranes  

International Nuclear Information System (INIS)

This study aims to investigate the difference in the interaction of antimicrobial peptides with two classes of zwitterionic peptides, phosphatidylethanolamines (PE) and phosphatidylcholines (PC). Further experiments were performed on model membranes prepared from specific bacterial lipids, lipopolysaccharides (LPS) isolated from Salmonella minnesota. The structure of the lipid-peptide aqueous dispersions was studied by small-and wide-angle X-ray diffraction during heating and cooling from 5 to 85 C. The lipids and peptides were mixed at lipid-to-peptide ratios 10-10000 (POPE and POPC) or 2-50 (LPS). All experiments were performed at synchrotron soft condensed matter beamline A2 in Hasylab at Desy in Hamburg, Germany. The phases were identified and the lattice parameters were calculated. Alamethicin and melittin interact in similar ways with the lipids. Pure POPC forms only lamellar phases. POPE forms lamellar phases at low temperatures that ...

3

Theory of zwitterionic molecular-based organic magnets  

British Library Electronic Table of Contents (United Kingdom)

We describe a class of organic molecular magnets based on zwitterionic molecules (betaine derivatives) possessing donor, p bridge, and acceptor groups. Using extensive electronic structure calculations we show the electronic ground-state in these systems is magnetic. In addition, we show that the large energy differences computed for the various magnetic states indicate a high Neel temperature. The quantum mechanical nature of the magnetic properties originates from the conjugated p bridge (only p electrons) in cooperation with the molecular donor-acceptor character. The exchange interactions between electron spin are strong, local, and independent on the length of the p bridge.

2011-01-01

4

Phosphatidic acid signaling to mTOR: Signals for the survival of human cancer cells  

UK PubMed Central (United Kingdom)

During the past decade elevated phospholipase D (PLD) activity has been reported in virtually all cancers where it has been examined. PLD catalyzes the hydrolysis of phosphatidylcholine to generate...Full Text Available

2009-09-01

5

Determination of bilayer membrane bending stiffness by tether formation from giant, thin-walled vesicles.  

UK PubMed Central (United Kingdom)

The curvature elastic modulus (bending stiffness) of stearoyloleoyl phosphatidylcholine (SOPC) bilayer membrane is determined from membrane tether formation experiments. R. E. Waugh and R. M. Hochmuth...Full Text Available

1989-03-01

6

Accelerated interleaflet transport of phosphatidylcholine molecules in membranes under deformation.  

UK PubMed Central (United Kingdom)

Biological membranes are lamellar structures composed of two leaflets capable of supporting different mechanical stresses. Stress differences between leaflets were generated during micromechanical experiments...Full Text Available

1996-09-01

7

Kinetics of carbon dioxide absorption in solutions of methyldiethanolamine  

Energy Technology Data Exchange (ETDEWEB)

The kinetics of the reaction of carbon dioxide in MDEA solutions were studied both experimentally and theoretically. It is concluded that MDEA acts as a homogeneous catalyst for CO/sub 2/ hydrolysis, and as a result the rate of absorption in aqueous MDEA solutions is significantly larger than one would calculate by simply taking into account the alkalinity of the reaction. A possible zwitterion mechanism is proposed for this reaction. The minor effect of ionic strength were also studied with the presence of other ions. 19 references, 6 figures.

1985-01-01

8

A zwitterionic silylene as reactive intermediate and its unusual dimerization to an N-heterobicyclic disilane.  

Science.gov (United States)

A way to synthesize the transient zwitterionic silylene L'Si: 8 {L'=CH[(C=CH(2))CMe(N(tBu))(2)]} and achieve its facile dimerization to the remarkable N-heterobicyclic disilane 8(2) is described. At first, employing the beta-diketiminate ligand L [L=CH(CMeN(tBu))(2)], both starting materials LH (2) and its N-lithium salt LLi (3) can react with SiBr(4) to yield the silylene precursor L'SiBr(2) (4) by silicon-induced C-H activation at an exocyclic methyl group on the backbone of the ligand. Compound 4 reacts with SiBr(4) above room temperature to afford the unexpected terminal CH(SiBr(3))-substituted dibromosilane 6 along with the unique tricyclic trisilane 7. Reduction of 4 with KC(8) at 0 degrees C furnishes the novel N-heterobicyclic disilane 8(2), which is a formal dimer of the desired zwitterionic silylene L'Si: (8). It has been reasoned that compound 8(2) may results from [4+1] cycloaddition of two molecules of 8 to give the transient dimer ...

2009-08-01

9

Structural characterization of liposomes made of diether archaeal lipids and dipalmitoyl-L-a-phosphatidylcholine  

British Library Electronic Table of Contents (United Kingdom)

The physicochemical properties of binary lipid mixtures of diether C25,25 lipids and dipalmitoyl-L-a-phosphatidylcholine (DPPC) were studied using photon correlation, fluorescence and electron paramagnetic resonance spectroscopy, and transmission electron microscopy. These two types of lipids can be mixed at all molar ratios to form unilamellar and multilamellar liposomes. Fluorescence anisotropy of 1,6-diphenyl-1,3,5-hexatrien in mixed liposomes indicates that the abrupt changes in order parameter in the hydrophobic part of bilayer membranes made of DPPC lipids disappears with increasing mol%C25,25 lipids. Electron paramagnetic resonance spectroscopy shows that at temperatures below 50^oC, the interfacial regions of membrane bilayer of mixed liposomes is more fluid than for pure DPPC lipo...

2011-01-01

10

Micropolarities of lipid bilayers and micelles. 3. Effect of monovalent ions on the dielectric constant of the water-membrane interface of unilamellar phosphatidylcholine vesicles  

Energy Technology Data Exchange (ETDEWEB)

A study was undertaken of the effect of monovalent cations (Li/sup +/, Na/sup +/, K/sup +/) on the dielectric constant (epsilon) of the water-lipid interface of unilamellar phosphatidylcholine (PC) vesicles, i.e., the ester carbonyl oxygen region of the PC molecules or the neighborhood of the oxygen atoms of the phosphorylcholine moiety. epsilon was determined by reacting the free radical 1,1-diphenyl-2-picrylhydrazyl with ..cap alpha..-tocopherol incorporated in the lipid vesicles. The results are consistent with a decrease of epsilon (LiCl: 35.5 to 29.5; NaCl: 34 to 29; KCl: 33 to 29) as the concentration of the salts in the solvent media increases from 0.025 to 0.5 M. These effects can be rationalized in terms of dielectric saturation at the water-lipid interface brought about by ion-induced local electric fields. In the unilamellar PC vesicles the effect of the ions on epsilon follows the sequence K/sup +/ > Na/sup +/ > Li/sup +/ which contrasts ...

1986-02-27

11

Ganglioside GM_1 spontaneous transfer between phospholipid vesicles  

International Nuclear Information System (INIS)

The transfer kinetics of the monosiaylated glycosphingolipid, GM_1, between different size phospholipid vesicles was measured using molecular sieve chromatography. At desired time intervals, small unilamellar donor vesicles were separated from large unilamellar acceptor vesicles by elution from a Sephacryl S-500 column ["3H]-GM_1 net transfer was calculated relative to ["1"4C]-cholesteryl oleate, which served as a nontransferable marker in the donor vesicles. The initial GM_1 transfer rate between 1-palmitoyl-2-oleoyl phosphatidylcholine vesicles at 45"0C deviated slightly from first order kinetics and possessed a half time of 3.6 days. This transfer half time is an order of magnitude shorter than that observed from the desiaylated derivative of GM_1. The transfer kinetics are consistent with the authors recent electron microscopic results suggesting a molecular distribution of GM_1 in liquid-crystalline phosphatidylcholine bilayers.

1986-06-08

12

Synthesis and Biophysical Characterization of Chlorambucil Anticancer Ether Lipid Prodrugs  

DEFF Research Database (Denmark)

The synthesis and biophysical characterization of four prodrug ether phospholipid conjugates are described. The lipids are prepared from the anticancer drug chlorambucil and have C16 and C18 ether chains with phosphatidylcholine or phosphatidylglycerol headgroups. All four prodrugs have the ability to form unilamellar liposomes (86-125 nm) and are hydrolyzed by phospholipase A2, resulting in chlorambucil release. Liposomal formulations of prodrug lipids displayed cytotoxicity toward HT-29, MT-3, and ES-2 cancer cell lines in the presence of phospholipase A2, with IC50 values in the 8-36 ?M range.

2009-01-01

13

Evaluation of the addition of various surfactant-suspended carbon nanotubes in MEEKC with an in situ-synthesized surfactant system  

British Library Electronic Table of Contents (United Kingdom)

Abstract Dispersions of single-walled carbon nanotubes (SWNTs) in various surfactant solutions have been systematically evaluated as additives in MEEKC. The compounds examined were catechins, phenolic acids, and flavonoids. Compared with zwitterionic and neutral surfactants, the addition of anionic dispersion seemed to be better at separating the three types of analytes in microemulsion system. In order to achieve low operating currents, an in situ-synthesized surfactant system based on the combination of a long-chain alkyl acid with an organic base was used in MEEKC. The optimized buffer contained 0.5% (57-mM) ethyl acetate, 0.6% (30-mM) lauric acid, 4.0% (666-mM) propanol, 50-mM Tris solution, and 4.5-mg/L the dispersion of SWNTs. Under optimized conditions, the established method was ap...

2011-01-01

14

New trends in phospholipid class composition of marine sponges  

British Library Electronic Table of Contents (United Kingdom)

The exceptional ability of marine sponges to adapt to often drastic changes of their environments could be due to special structural features in cell membranes, including firstly phospholipids (PL). Thus, PL class composition was investigated in marine sponges (22 species from 19 genera to 15 families) originating from various locations (East Atlantic, North Atlantic, South-West Pacific, Mediterranean Sea, Red Sea, Arabian?Persian Gulf). The quantitative determination of PL class composition was obtained by high-performance thin-layer chromatography (HPTLC) with scanning densitometry of the different spots. Previous reports have shown phosphatidylethanolamine (PE) as the major PL class in marine sponges, followed by phosphatidylcholine (PC), while other papers described PC as a minor class...

2008-01-01

15

Temperature-induced fusion of small unilamellar vesicles formed from saturated long-chain lecithins and diheptanoylphosphatidylcholine  

Energy Technology Data Exchange (ETDEWEB)

Small unilamellar vesicles which form when gel-state long-chain phosphatidylcholines are mixed with micellar short-chain lecithins undergo an increase in size as the long-chain species melts to its liquid-crystalline form. Analysis of the vesicle population with quasi-elastic light scattering shows that the particle size increases from 90-A radius to greater than 5000-A radius. Resonance energy transfer experiments show total mixing of lipid probes with unlabeled vesicles only when the Tm of the long-chain phosphatidylcholine is exceeded. This implies that the large size change represents a fusion process. Aqueous compartments are also mixed during this transition. 31P NMR analysis of the vesicle mixtures above the phase transition shows a great degree of heterogeneity with large unilamellar particles coexisting with oligo- and multilamellar structures. Upon cooling the vesicles below the Tm, the original size distribution (e.g., small ...

1989-10-03

16

Synthesis and characterization of diastereomeric (substituted iminodiacetato)(1,2-diaminocyclohexane)platinum(II) complexes  

Energy Technology Data Exchange (ETDEWEB)

Novel complexes of the type (Pt(DACH)(N-R-iminodiacetate)), wherein DACH represents (R,S)- and (R,R)-1,2 diaminocyclohexane and R represents /minus/Me, /minus/EtOH, and /minus/CH/sub 2/Ph groups, have been prepared, purified, and characterized by spectroscopic techniques (/sup 1/H, /sup 13/C, and /sup 195/Pt NMR;MS(FAB);IR) and by the measurement of selected physical properties (pH, pK/sub a/, conductivity, and molecular weights). The data are consistent with the formation of two diastereomeric complexes in unequal proportions in which the N-R-iminodiacetate ligand appears to be bonded as a pseudofacial tridentate chelate. One are of the ligand forms a stable five-membered-ring O,N-chelate while the other arm appears to be involved in ion-pair formation (zwitterion-like) involving the carboxylate anion and the formally positive Pt(II) central metal atom. It has been demonstrated indirectly that an active impurity was present in predictably inactive bulk complexes ...

1988-11-16

17

Metal coordination and selectivity with oxine ligands bound to silica polyamine composites  

British Library Electronic Table of Contents (United Kingdom)

A series of oxine ligands, 5-X, 8 OH C9H6N (X = H, Cl, SO3H) have been covalently bound to a silica gel polyamine composite made from a silanized amorphous silica xerogel and poly(allylamine) (BP-1) by the Mannich reaction. The resulting modified composites WP-4(X = H), CB-1(X = Cl), and SB-1(X = SO3H) were characterized by elemental analysis, FTIR, and solid state CPMAS-13C-NMR. Using the analytical data before and after the ligand modification, the ligand loading could be estimated and in combination with metal ion capacities a metal to ligand ratio could be obtained. The composites WP-4 and CB-1 both showed ratios of approximately 1 : 1 while the sulfonate modified composite, SB-1, showed a metal to ligand ratio of 1 : 2. This is tentatively interpreted in terms of a zwitterionic oxine ...

2010-01-01

18

Antibiotic interaction with phospholipid monolayers  

Energy Technology Data Exchange (ETDEWEB)

We studied the interactions of tetracycline (TC) antibiotic molecules with phospholipid monolayers with the two-fold aim of elucidating the mechanism of action and providing a first step for the realization of bio-mimetic sensors for such drugs by means of the Langmuir-Blodgett technique. We examined spreading monolayers of three phospholipids in the presence of tetracycline in the subphase by means of surface pressure-area and surface potential-area isotherms as a function of bulk pH. We selected phospholipids with hydrophobic chains of the same length but polar head groups differing either in dimensions and protonation equilibria, i.e. dipalmitoylphosphatidylcholine (DPPC), dipalmitoylphosphatidylethanolamine (DPPE) and dipalmitoylphosphatidic acid (DPPA). The interaction of tetracycline with the three phospholipids was found to be highly dependent on the electric charge of the antibiotic and on the ionization state of the lipid. Significant interactions are established between the ...

2002-12-01

19

Systematic implicit solvent coarse-graining of bilayer membranes: lipid and phase transferability of the force field  

International Nuclear Information System (INIS)

We study the lipid and phase transferability of our recently developed systematically coarse-grained solvent-free membrane model. The force field was explicitly parameterized to describe a fluid 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC) bilayer at 310 K with correct structure and area per lipid, while gaining at least three orders of magnitude in computational efficiency (see Wang and Deserno 2010 J. Phys. Chem. B 114 11207-20). Here, we show that exchanging CG tails, without any subsequent re-parameterization, creates reliable models of 1,2-dioleoylphosphatidylcholine (DOPC) and 1,2-dipalmitoylphosphatidylcholine (DPPC) lipids in terms of structure and area per lipid. Furthermore, all CG lipids undergo a liquid-gel transition upon cooling, with characteristics like those observed in experiments and all-atom simulations during phase transformation. These studies suggest a promising transferability of our force field parameters to different lipid species and ...

2010-09-01

20

Lipid domain formation modulates activities of snake venom phospholipase A(2) enzymes.  

Science.gov (United States)

The goal of the present study is to elucidate the effect of lipid domain formation on activities of Naja naja atra and Bungarus multicinctus phospholipase A(2) (PLA(2)) enzymes. Sphingomyelin inhibited enzymatic activity and membrane-damaging activity of PLA(2) against egg yolk phosphatidylcholine (EYPC), while cholesterol and cholesterol sulfate abrogated the inhibitory effect of sphingomyelin. The ability of cholesterol and cholesterol sulfate to abolish the inhibitory effect of sphingomyelin was closely related to their capacity to induce domain formation in EYPC/sphingomyelin vesicles. Laurdan fluorescence measurement revealed that membrane packing of EYPC/sphingomyelin vesicles was differently affected by cholesterol and cholesterol sulfate. Unlike cholesterol, cholesterol sulfate was unable to promote domain formation in dipalmitoylphosphatidylcholine (DPPC) vesicles. Cholesterol increased but cholesterol sulfate reduced PLA(2) activity against DPPC. ...

2010-08-10

 
 
 
 
21

Evaluation of small-angle neutron scattering curves of unilamellar phosphatidylcholine liposomes using a multi shell model of bilayer neutron scattering length density  

International Nuclear Information System (INIS)

Computer simulated small-angle neutron scattering curves of spherical poly disperse extruded unilamellar liposomes from saturated 1,2-diacylphosphatidylcholines in the aqueous phase are evaluated by using a multi shell model, which divides the lipid bilayer of liposomes into the polar head group region, and the nonpolar hydrocarbon region consisting of the chains of methylene groups and of the region of methyl groups. In the each of these regions, the coherent neutron scattering length density is supposed to by homogeneous. The evaluation is based on obtaining of radius of gyration from Kratky-Porod plot of small-angle neutron scattering data in the Guinier region of small scattering vector values. From radii of gyration obtained at several different molar fractions N_D_2_O/(N_D-2_O + N_H_2_O) in the aqueous phase (contrasts) and independent volumetric data, the lipid surface area A_L (or the bilayer thickness d_L) and the number of water molecules N_L penetrated into the bilayer polar ...

2000-12-15

22

Detection of Cholangiocarcinoma with Magnetic Resonance Spectroscopy of Bile in Patients with and without Primary Sclerosing Cholangitis  

International Nuclear Information System (INIS)

Background: Early detection of cholangiocarcinoma (CC) is very difficult, especially in patients with primary sclerosing cholangitis (PSC) who are at increased risk of developing CC. Purpose: To evaluate "1H magnetic resonance spectroscopy ("1H-MRS) of bile as a diagnostic marker for CC in patients with and without PSC. Material and Methods: The institutional review board approved the study, and all patients gave informed consent. Bile from 49 patients was sampled and investigated using "1H-MRS. MR spectra of bile samples from 45 patients (18 female; age range 22-87 years, mean age 57 years) were analyzed both conventionally and using computerized multivariate analysis. Sixteen of the patients had CC, 18 had PSC, and 11 had other benign findings. Results: The spectra of bile from CC patients differed from the benign group in the levels of phosphatidylcholine, bile acids, lipid, and cholesterol. It was possible to distinguish CC from benign conditions in all ...

2008-10-01