Dilute Bicellar Solutions for Structural NMR Work

Deuterium NMR spectroscopy has been employed to characterize the concentration dependence of orientational order in DMPC/DHPC bicellar solutions with molar ratiosq= [DMPC]/[DHPC] = 3.3, 2.7, and 2.3. The stability of a discotic nematic phase can, in general, be predicted from a simple Onsager picture involving the size and concentration of the mesogenic unit, but for the bicellar solutions this model is not adequate. Specifically, macroscopic alignment is observed at total lipid concentrations well below that, 1–10% (w/w) predicted by Onsager's model. Thus the discotic nematic phase is stable to ≈3–5% (w/w) forq= 3.3–2.3, and the bicellar order is highest just before phase separation occurs at the minimum total phospholipid concentration. This implies the presence of a DHPC_bic DHPC_solequilibrium in establishing bicellar size, thereby extending the range of concentrations for which alignment occurs. Bicellar morphology has been verified for a wide range of concentrations, temperatures, andq-values, but as viscosity measurements demonstrate, major morphological changes take place as the temperature is reduced below 30°C.     

Derivative enzymatic–spectrophotometric method for choline containing phospholipid determination in human serum, bile and amniotic fluid: recovery data by ‘standard addition’ method

Unpublished analytical data obtained by recovery tests by ‘standard addition’ method, concerning lecithin determinations in human serum, bile and amniotic fluid, using new derivative enzymatic–spectrophotometric method, recently pointed out by the authors, are reported and shortly discussed.     

Mimicking Photosystem I with a Transmembrane Light Harvester and Energy Transfer-Induced Photoreduction in Phospholipid Bilayers

Photosystem I (PS I) is a transmembrane protein that assembles perpendicular to the membrane, and performs light harvesting, energy transfer, and electron transfer to a final, water-soluble electron acceptor. We present here a supramolecular model of it formed by a bicationic oligofluorene 1²⁺ bound to the bisanionic photoredox catalyst eosin Y (EY²⁻) in phospholipid bilayers. According to confocal microscopy, molecular modeling, and time dependent density functional theory calculations, 1²⁺ prefers to align perpendicularly to the lipid bilayer. In presence of EY²⁻, a strong complex is formed (K_a=2.1±0.1×10⁶ m ⁻¹), which upon excitation of 1²⁺ leads to efficient energy transfer to EY²⁻. Follow-up electron transfer from the excited state of EY²⁻ to the water-soluble electron donor EDTA was shown via UV–Vis absorption spectroscopy. Overall, controlled self-assembly and photochemistry within the membrane provides an unprecedented yet simple synthetic functional mimic of PS I.     

In vitro and in vivo stability of polymerized mixed liposomes composed of 2,4‐octadecadienoyl groups of phospholipids

The in vitro stability, under freeze–thawing procedures, and in vivo degradation, in rat spleen, of two types of polymerized liposomes were examined: 1,2‐bis‐[2E, ­4E) ‐ octadecadienoyl] ‐ sn ‐ glycero ‐ 3 ‐ phosphocholine (DODPC) and 1‐acyl‐2‐[(2E, 4E)‐octadecadienoyl]‐sn‐glycero‐3‐phosphocholine (AODPC) were used as polymerizable phospholipids. The lipid composition of the liposomes was prepared as DODPC/Chol/SA (Chol = cholesterol, SA = stearicacid), AODPC/Chol/SA (7/7/2 by molar ratio), AODPC/DPPC/Chol/SA (3.5/3.5/7/2 by molar ratio). The liposomes were extruded through a 0.2 µm polycarbonate‐ filter to obtain the approximate particle size of 0.2 µm, and then irradiated with γ‐rays. Hemoglobin‐encapsulated liposomes were also prepared in the same manner with concentrated hemoglobin (Hb) solution. The DODPC/Chol/SA liposome exhibited no trace of particle size change nor Hb leakage. Although not as excellent as the former, the AODPC‐base liposome showed slightly diameter change (below 7.5%) with a substantial abatement of Hb leakage (<3.5%). Transmission electron microscopy observation of spleens also revealed more efficient degradability with AODPC/DPPC/Chol/SA liposome than with DODPC/Chol/SA liposome. Hb‐encapsulated AODPC/DPPC/Chol/SA liposome, after five freeze–thawing cycles, attained an Hb leakage below 3.5% with a particle size change of 0.7–7.5%, and reduced the spleen retention compared with the DODPC‐base liposome. These results suggest that AODPC/DPPC/Chol/SA liposome can be used as a long‐term preservable blood substitute. Copyright © 2000 John Wiley & Sons, Ltd.     

United atom force field for phospholipid membranes: Constant pressure molecular dynamics simulation of dipalmitoylphosphatidicholine/water system

We refined the united atom field for the simulations of phospholipid membranes. To validate this potential we performed 1000-ps constant pressure simulation of a dipalmitoylphosphatidicholine (DPPC) bilayer at T=50° C. The average area per head group (61.6±0.6) Ų obtained in our simulation agrees well with the measured one of (62.9±1.3) Ų. The calculated S_CD order parameters for the Sn-2 hydrocarbon tail also display a good agreement with the experiment. The conformations of head groups in our simulations of the liquid crystal phase are different than the ones observed in the crystal structure. ©1999 John Wiley & Sons, Inc. J Comput Chem 20, 531–545, 1999     

Studies on syntheses and properties of novel polyamides containing phosphatidylcholine analogous moieties by interfacial polycondensation

Polyamides (4a-b and 5a-b) were synthesized from interfacial polycondensation of novel diamine containing phosphatidylcholine analogous moiety, hexamethylene diamine with adipoyl chloride, or sebacoyl chloride in the interface of water and carbon tetrachloride at room temperature. The characterizations of synthesized diamine and polyamides were carried out with FT-NMR, or IR spectral method, elemental analysis, and melting point measurements, respectively. These polyamides obtained are insoluble in any normal solvents. From the results of X-ray diffraction analysis and POM observation, it was revealed that the polyamide 4b was prepared with high molecular weight, while polyamide 4a obtained seemed to have low molecular weight. For copolymers 5a and 5b, X-ray reflections from only adipoyl or sebacoyl chloride parts were observed as in crystalline state. In addition, thermal properties were also studied by DSC and transmitted light intensity measurements. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3065–3074, 1997     

Au/硫醇/卵磷脂双层膜的制备及其电化学表征

生命体系的许多过程发生在生物膜上,生物膜模拟体系的制备与研究一直受到人们的重视．自组装单分子膜（ＳｅｌｆＡｓｅｍｂｌｅｄＭｏｎｏｌａｙｅｒｓ,ＳＡＭｓ）特别是在金基底表面的硫醇单分子膜由于其具有良好的稳定性及有序性,因此在基础理论研究及应用技术等方...     

DMPC与蛋白质在气-液界面上复合组装过程研究

对磷脂DMPC与蛋白质(β-lactoglobulin,β-casein或humanserumalbumin)组成的复合单分子膜在压缩过程中的相变进行了研究,同时通过Brewster角显微镜观察了磷脂与蛋白质在空气-水界面处发生的自组装过程。发现当低表面压时在DMPC/β-casein,DMPC/humanserumalbumin和DMPC/β-lactoglobulin复合单分子膜上分别出现线状和块状微区,而在较高表面压时只有DMPC/β-casein体系出现钩状的微区。说明微区的形貌与蛋白质的种类及构象变化有关。     

DNA—metal(ii) ion—phosphatidylcholine complexes: structure calculations and stability estimates by molecular mechanics

The structures and formation energies of nucleic acid—phospholipid complexes both in the absence and in the presence of Mg²⁺ ions were calculated taking double-stranded trinucleoside diphosphates NpNpN or heptanucleotides ApAp(NpNpN)pApA, composed of 64 possible combinations of genetic code, and phosphatidylcholine as model compounds. The dependence of intramolecular interactions on the primary structure of nucleic acid molecules and on the presence of a cationic bridge was revealed. The formation energies and structure of oligonucleotides were found by molecular mechanics calculations with the AMBER force field. The structures of phospholipid and MgCl₂ molecules were calculated by the semiempirical PM3 method, while the energies of phospholipid—oligonucleotide complexes were calculated by the molecular mechanics method. Calculations of complexes were carried our with consideration of solvation effects. Considerable gain in the formation energy of triple complexes (13–14 kcal mol⁻¹) is achieved due to the presence of the electroneural metal bridge. A tendency toward increasing the stability of triple complexes containing guanosine-and cytidine-enriched triplets was revealed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2068–2071, November, 1999.     

Comparative Study of Preparation,Evaluation, and Pharmacokinetics in Beagle Dogs of Curcumin β-Cyclodextrin Inclusion Complex,Curcumin Solid Dispersion,and Curcumin Phospholipid Complex

Curcumin is a natural acidic polyphenol extracted from turmeric with a wide range of biological and pharmacological effects. However, the application of curcumin for animal production and human life is limited by a low oral bioavailability. In this study, natural curcumin was prepared for the curcumin β-cyclodextrin inclusion complex (CUR-β-CD), curcumin solid dispersion (CUR-PEG-6000), and curcumin phospholipid complex (CUR-HSPC) using co-precipitation, melting, and solvent methods, respectively. Curcumin complex formations were monitored using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) techniques via the shifts in the microscopic structure, molecular structure, and crystalline state. Subsequently, twenty-four female beagle dogs were randomly divided into four groups to receive unmodified curcumin and three other curcumin preparations. The validated UPLC–MS assay was successfully applied to pharmacokinetic and bioavailability studies of curcumin in beagle dog plasma, which were collected after dosing at 0 min (predose), 5 min, 15 min, 30 min, 40 min, 50 min, 1.5 h, 3 h, 4.5 h, 5.5 h, 6 h, 6.5 h, 9 h, and 24 h. The relative bioavailabilities of CUR-β-CD, CUR-PEG-6000, and CUR-HSPC were 231.94%, 272.37%, and 196.42%, respectively. This confirmed that CUR-β-CD, CUR-HSPC, and especially CUR-PEG-6000 could effectively improve the bioavailability of curcumin.