Transbilayer complementarity of phospholipids. Proof of principle

A series of nearest-neighbor recognition (NNR) experiments have been carried out, which provide a rigorous test of the existence of transbilayer complementarity of phospholipids, that is, the ability of phospholipids to select complementary phospholipids from an adjoining monolayer as nearest neighbors. The application of this test to membranes derived from exchangeable phospholipids bearing myristoyl groups (A), stearoyl groups (B), and one stearoyl and one n-dodecyl group (C) in the presence of analogous nonexchangeable templates made from A', B' and C' provides compelling evidence for such complementarity in the physiologically relevant fluid phase.     

Dipentaerethrite in the synthesis of model amidophosphate phospholipids

A productive method for the synthesis of original phospholipid architectures is developed based on the available reagent dipentaerythritol. Introduction of the phosphoric function to the system is achieved by using phosphoric hexaethyltriamide.     

Estimation of amniotic fluid phospholipids by high-performance liquid chromatography

We have developed a high-performance liquid chromatographic (HPLC) method for the analyses of surface-active amniotic fluid phospholipids, lecithin (L), sphingomyelin (S), phosphatidyl glycerol (PG), phosphatidyl inositol (PI), phosphatidyl ethanolamine (PE), and phosphatidyl serine (PS), which are important in the prediction of fetal lung maturity. The method incorporates an internal standard in the amniotic fluid extract, and utilizes a 10-microliter aliquot of a 2:1 chloroform-methanol extract of amniotic fluid injected onto a 5-micron DIOL or CN HPLC column, and a variable-wavelength detector set at 203 nm. Amniotic fluid phospholipid estimations were determined on 40 amniotic fluid samples by the HPLC method and by the routine thin-layer chromatographic (TLC) method. Good agreement was observed between the two methods for the L/S ratio, PG, and PI (rPG 0.94, rPI 0.95, rL/S 0.97). The advantages of the HPLC procedure include: Selective separation for PG, PI, PS, and PE, as well as L and S at the same time. The internal standard allows individual concentration of phospholipids to be estimated. The procedure is rapid: 16 min for a single assay compared with 50 min for the standard TLC procedure.     

Transport coefficients of the Lennard-Jones model fluid. I. Viscosity

In an extensive computer simulation study, the transport coefficients of the Lennard-Jones model fluid were determined with high accuracy from equilibrium molecular-dynamics simulations. In the frame of time-correlation function theory, the generalized Einstein relations were employed to evaluate the transport coefficients. This first of a series of four papers presents the results for the viscosity, and discusses and interprets the behavior of this transport coefficient in the fluid region of the phase diagram. Moreover, the kinetic-kinetic, kinetic-potential, and potential-potential viscosity contributions are resolved over the whole range of fluid states, and their characteristic dependence on temperature and density is described. Finally, an additional analysis of the shear-stress correlation functions reveals aspects of the momentum-transport mechanisms on the molecular scale.     

An evaluation of acid digestion methods for amniotic fluid phospholipids

Five methods of acid digestion of amniotic fluid phospholipids for inorganic phosphate release were evaluated at a temperature of 225 °C and a heating time of 30 min. The methods used the following digestants: (A (perchloric acid), B (perchloric acid containing molybdate), C (sulfuric acid, 30% hydrogen peroxide, 5% urea), D (sulfuric-perchloric acids), and E (sulfuric-perchloric acids with vanadium pentoxide). After digestion and dilution with water, a hydrogen ion concentration of about 2.5 mol/ liter was obtained that permitted the use of stannous chloride-hydrazine sulfate as the reducing agent for phosphate color development. Recoveries of the different amniotic fluid phospholipids and aqueous phosphate standards were quantitative for all methods. A comparative study with amniotic fluids showed similar results for all methods. Since all methods were found to be equivalent under the specified conditions described, the choice was dependent upon the user's preference.     

Predissociation of chlorobenzene, beyond the pseudo-diatomic model

Dissociation of chlorobenzene via the lowest singlet excited state has been investigated by means of pump–probe femtosecond spectroscopy and spin–orbit corrected ab initio quantum chemistry. We have found that the so far accepted model with a ¹ππ^* → ³π/nσ^* reaction mechanism has to be amended. We suggest that the mechanism goes via a transition from ¹ππ^* to a πσ^* state that is to 90% a singlet. Further, three nuclear degrees of freedom required to describe the dissociation have been defined.     

High pressure liquid chromatography of standard and amniotic fluid phospholipids

A method for the HPLC separation of phosphatidylglycerol (PG), phosphatidylinositol (PI), phosphatidylcholine (PC), and sphingomyelin (SPH) was achieved using five in-series columns packed with LiChrosorb, Partisil, and μ-Porasil adsorbents, a solvent mixture of chloroform/methanol/ammonium hydroxide (50 : 36 : 6.7, by volume), and a Pye LCM2 Moving Wire (FID) detector. The same phospholipid mixture was also separated using four μ-Porasil columns with the same eluent and detector. The latter conditions were found to be suitable for the analysis of phospholipids obtained after centrifuging, extraction, and precipitation of surface-active lipid components of patient amniotic fluid collected at amniocentesis section. The lecithin/sphingomyelin (L/S) ratios, determined by the HPLC method, correlated well with those determined by the TLC technique in four normal pregnancies, whereas results of shake tests did not correlate too well with L/S ratios determined by the above two chromatographic methods. Besides the lecithin/sphingomyelin ratio, the present method was able to supply additional information: the concentrations of phosphatidylglycerol and phosphatidylinositol, for prediction of fetal lung maturity, and the palmitic acid content of amniotic fluid phosphatidylcholine.     

Moving beyond message passing. Experiments with a distributed-data model

Summary A message-passing model provides a natural and efficient parallel implementation for many applications in chemical physics on MIMD machines. However, although the distinction between local and non-local memory is at the very heart of writing efficient parallel programs, message passing leaves all responsibility for data management to the applications. This has significant, detrimental implications for both ease of programming and efficient use of shared and distributed resources. Examined here is a simple model which increments message passing with Linda-like tools for the manipulation of distributed-data structures. This is applied to common algorithms in chemical physics.     

Transport coefficients of the Lennard-Jones model fluid. II Self-diffusion

In an extensive computer simulation study, the transport coefficients of the Lennard-Jones model fluid were determined with high accuracy from equilibrium molecular-dynamics simulations. In the frame of time-correlation function theory, the generalized Einstein relations were employed to evaluate the transport coefficients. This second of a series of four papers presents the results for the self-diffusion coefficient, and discusses and interprets the behavior of this transport coefficient in the fluid region of the phase diagram. The uncertainty of the self-diffusion data is estimated to be 1% in the gas region and 0.5% at high-density liquid states. With the very accurate data, even fine details in the shape of the self-diffusion isotherms are resolved, and the previously little-investigated behavior of the self-diffusion coefficient at low-density gaseous states is analyzed in detail. Finally, aspects of the mass transport mechanisms on the molecular scale are explored by an analysis of the velocity autocorrelation functions.     

Transport coefficients of the Lennard-Jones model fluid. III. Bulk viscosity

In an extensive computer simulation study, the transport coefficients of the Lennard-Jones model fluid were determined with high accuracy from equilibrium molecular-dynamics simulations. In the frame of time-correlation function theory, the generalized Einstein relations were employed to evaluate the transport coefficients. This third of a series of four papers presents the results for the bulk viscosity. With comprehensive simulation data at over 350 state points, the temperature and density dependences of the bulk viscosity are characterized in this work over a wide range of fluid states. The bulk viscosity exhibits a large critical enhancement similar to that known for the thermal conductivity, but it extends much farther into the supercritical region and can be observed even at 4.5 times the critical temperature. An investigation of the pressure-fluctuation autocorrelation functions shows that the enhancement is caused by extremely slowly decaying pressure fluctuations.     

Quantitative determination of phospholipids in amniotic fluid by high-performance liquid chromatography

Summary A new quantitative analytical method for the determination of phospholipids in amniotic fluid by high performance liquid chromatography (HPLC) is described. In addition to the main compounds, phosphatidylcholine (lecithin) and sphingomyelin, the so-called minor phospholipids, phosphatidylglycerol, phosphatidylinositol and phosphatidylethanolamine can also be determined. Separation is achieved using a guard-column of Lichrosorb Si 60 and an analytical column of Lichrosorb DIOL. Acetonitrile/water is used as mobile phase at an elevated temperature. By determining the recovery rates, the within-run and the between-run precision, it was shown that sufficient accuracy and precision could be achieved for all the parameters examined. The method is highly sensitive, the detection limit for sphingomyelin is 0.2 μg and 0.1 μg for all the other components. A single determination of 5 phospholipids in an amniotic fluid sample takes about two hours. By performing simultaneous extractions it is possible to analyse 5 samples per day.     

A study of the phospholipids of kenaf

Summary The fatty-acid composition of the combined phospholipids and also of the main and two minor components of the phospholipids have been studied. On the basis of the results of acid hydrolysis and also IR spectroscopy, the glycerophospholipid structure of the main components of the total material has been confirmed. These main components have been subjected to enzymatic hydrolysis: the position distribution of the fatty acids have been determined and, from these, the possible diglyceride compositions of the phosphatidylcholines, phosphatidylethanolamines, and phosphatidylinositols have been calculated. It has been shown that the phospholipids are accompanied by 35–40% of carbohydrates which have been characterized qualitatively as disaccharides.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 289–293, May–June, 1976.     

On the fluid phase behaviour of fluid binary mixtures using the Yukawa fluid molecular model

By expanding Ginoza’s mean spherical approximation (MSA) results in an inverse-temperature expansion, Henderson et al. obtained explicit results for the thermodynamic functions of a pure Yukawa fluid. We have recently published explicit results for the coefficients in an inverse-temperature expansion of the thermodynamic functions for the MSA for mixtures of Yukawa fluids. Attention is drawn to the fact that the MSA in the Ginoza formulation, does not always yield a convergent solution. The expansion used in this paper will always yield a result. In this work we present our investigations of the fluid phase diagram of Yukawa binary mixtures by considering an expansion of the MSA Helmholtz free energy up to the fifth order of the inverse-temperature expansion. The calculated fluid phase diagrams for Yukawa binary mixtures are similar to those of real mixtures.     

Steric nature of the bite angle. A closer and a broader look

The bite angle (ligand-metal-ligand angle) is known to greatly influence the activity of catalytically active transition-metal complexes towards bond activation. Here, we have computationally explored how and why the bite angle has such effects in a wide range of prototypical C-X bonds and palladium complexes, using relativistic density functional theory at ZORA-BLYP/TZ2P. Our model reactions cover the substrates H(3)C-X (with X = H, CH(3), Cl) and, among others, the model catalysts, Pd[PH(2)(CH(2))(n)PH(2)] (with n = 2-6) and Pd[PR(2)(CH(2))(n)PR(2)] (n = 2-4 and R = Me, Ph, t-Bu, Cl), Pd(PH(3))X(-) (X = Cl, Br, I), as well as palladium complexes of chelating and non-chelating N-heterocyclic carbenes. The purpose is to elaborate on an earlier finding that bite-angle effects have a predominantly (although not exclusively) steric nature: a smaller bite angle makes more room for coordinating a substrate by bending away the ligands. Indeed, the present results further consolidate this steric picture by revealing its occurrence in this broader range of model reactions and by identifying and quantifying the exact working mechanism through activation strain analyses.     

A comparative study of the phospholipids of kenaf seeds

Summary The qualitative and qualitative compositions of the phospholipids of kenaf seeds of the variety Opytnyi-1961 have been investigated. It has been established that the main components of the total phospholipids are phosphatidylcholines, phosphatidylethanolamines, and phosphatidylinositols, and minor components are N-acyl-PEs and their lyso analogs The structural analysis of these homogeneous fractions has been performed, and the molecular compositions of the main fractions have been calculated. On comparing the results obtained with those of other varieties of kenaf investigated previously, some differences have appeared in the qualitative, quantitative, molecular, and fatty-acid compositions of the total phospholipids and of individual fractions of them.The differences found are possibly due to the variety of characteristics of the plant. For the N-acyllyso-PEs the structure of 2-acylglycerophosphoryl-N-acylethanolamines has been established.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 559–562, September–October, 1978.