聚乙烯吡咯烷酮/聚(乙烯-乙烯醇)共混膜的制备及其油水分离性能

将聚乙烯吡咯烷酮(PVP)与聚(乙烯-乙烯醇)(EVAL)共混,采用浸没沉淀法制备了PVP/EVAL共混膜,并用于油水乳液分离过程。通过全反射红外光谱、扫描电子显微镜、拉伸试验、接触角测试等对膜的组成、结构形态、机械性能、亲水性进行了表征,并研究了PVP添加量对共混膜油水分离性能的影响。结果表明:添加PVP能较显著地改变EVAL膜的结构,且共混膜的机械强度和亲水性得到明显改善,当PVP添加量为10 wt%(PVP在铸膜液中的质量分数)时,其拉伸强度和断裂伸长率分别为纯EVAL膜的1.88倍和1.34倍。当PVP添加量为4 wt%时,油水分离稳定通量为纯EVAL膜的1.81倍,截留率为92.2%,比纯EVAL膜略高。PVP添加量为10 wt%的PVP/EVAL共混膜清洗后通量恢复率由纯EVAL膜的51%增至77.98%。     

Use of attenuated total reflectance Fourier transform infrared spectroscopy to monitor the development of lipid aggregate structures

Attenuated total reflectance Fourier transform infrared spectroscopy is used to monitor the adsorption of 100 nm 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) phospholipid vesicles to the surfaces of Ge, electrolessly deposited Au, and a well formed self-assembled monolayer of 1-octadecanethiol. The interaction of DPPC vesicles in solution with these different surfaces yields distinctly different surface structures: intact DPPC vesicles on Ge, a supported phospholipid bilayer on an electrolessly deposited Au surface, and a phospholipid monolayer onto the hydrophobic self-assembled monolayer. IR peak position, bandwidth, and intensity are used to confirm structure formation and quantitation of the amount of lipid that desorbs during film formation.     

Interaction of Soybean Oil with Phosphatidylcholine and Their Formation of Small Dispersed Particles

Stable aqueous dispersions of soybean oil (SO) were obtained by cosonication with dipalmitoylphosphatidylcholine (DPPC) in the SO mole fraction range 0.1–0.8. To clarify the dispersal mechanism, the dispersed particles were characterized, and the interaction between SO and DPPC was investigated using several physicochemical techniques. Dynamic light scattering (DLS) measurements showed that the diameter of the dispersed particles was 40–60 nm. The trapped aqueous volume inside the particles was determined fluorometrically using the aqueous space marker calcein. The trapped volume in the SO/DPPC particles decreased remarkably with the addition of SO into small unilamellar vesicles of DPPC. The decline in fraction of vesicular particles was also confirmed by fluorescence quenching of N-dansylhexadecylamine in the DPPC membrane by the addition of the quencher CuSO₄. These results indicate that the excess SO separated from the DPPC bilayers is stabilized as emulsion particles by the DPPC surface monolayer. Monolayer-bilayer equilibrium of SO/DPPC mixtures was estimated by measurement of spreading and collapse pressures. The results showed that the coexistence of emulsion particles (surface monolayer of DPPC + core of SO) with vesicular particles (bilayer) was critically important for the formation of stably dispersed particles of the lipid mixture.     

Proton transfer in time-of-flight secondary ion mass spectrometry studies of frozen-hydrated dipalmitoylphosphatidylcholine

A frozen water matrix, as found in freeze-fractured frozen-hydrated cellular samples, enhances the ionization of phosphatidylcholine lipids with static time-of-flight secondary ion mass spectrometry (TOF-SIMS). Isotopic profiles of the phosphocholine ion from deuterated forms of dipalmitoylphosphatidylcholine (DPPC) have been examined under various sample preparation conditions to show that ionization occurs through protonation from the matrix and is enhanced by the water present in freeze-fractured samples. The ionization of DPPC results in positively charged fragment ions, primarily phosphocholine, with a m/z of 184. Other ions include the M + H ion (m/z 735) and an ion representing the abstraction of the two palmitoyl fatty acid groups (m/z 224). Freeze-fracture techniques have been used to prepare frozen aqueous samples such as liposomes and cells to expose their membranes for static TOF-SIMS imaging. Due to the importance of surface water during SIMS analyses, sources of gas-phase water resulting from freeze-fracture were examined. Under proper fracturing conditions, water vapor, resulting from water in the sample and water condensed onto the outside of the sample, is released into the vacuum but does not condense back onto the surface. Combining the demonstrated enhancement of phosphatidylcholine lipid signal from water with the freeze-fracture preparation techniques described herein demonstrates potential advantages of studying biological samples in a frozen-hydrated state.     

Interaction of soybean oil with phosphatidylcholine and their formation of small dispersed particles

Stable aqueous dispersions of soybean oil (SO) were obtained by cosonication with dipalmitoylphosphatidylcholine (DPPC) in the SO mole fraction range 0.1-0.8. To clarify the dispersal mechanism, the dispersed particles were characterized, and the interaction between SO and DPPC was investigated using several physicochemical techniques. Dynamic light scattering (DLS) measurements showed that the diameter of the dispersed particles was 40-60 nm. The trapped aqueous volume inside the particles was determined fluorometrically using the aqueous space marker calcein. The trapped volume in the SO/DPPC particles decreased remarkably with the addition of SO into small unilamellar vesicles of DPPC. The decline in fraction of vesicular particles was also confirmed by fluorescence quenching of N-dansylhexadecylamine in the DPPC membrane by the addition of the quencher CuSO₄. These results indicate that the excess SO separated from the DPPC bilayers is stabilized as emulsion particles by the DPPC surface monolayer. Monolayer-bilayer equilibrium of SO/DPPC mixtures was estimated by measurement of spreading and collapse pressures. The results showed that the coexistence of emulsion particles (surface monolayer of DPPC + core of SO) with vesicular particles (bilayer) was critically important for the formation of stably dispersed particles of the lipid mixture.     

油水相界面张力对乳化炸药性能的影响

采用白金环法测定了乳化炸药复合油相与硝酸铵水溶液的界面张力,并研究了乳化剂质量分数、温度、分子结构和热值对油水相界面张力的影响以及界面张力对乳胶基质微观结构和储存稳定性的影响。结果表明,随着乳化剂质量分数的升高,界面张力先下降后保持恒定;随着温度升高,界面张力呈线性下降趋势;复合蜡组分的异构化烷烃含量越高,环状化合物越少,热值越低,油水相界面张力越低。随着界面张力和临界质量分数的降低,乳胶基质的粒径减小。乳胶基质的储存稳定性随着油相材料界面张力的降低而增强。     

Optical trapping of unilamellar phospholipid vesicles: investigation of the effect of optical forces on the lipid membrane shape by confocal-Raman microscopy

Optical trapping of liposomes is a useful tool for manipulating these lipid vesicles for sampling, mechanical testing, spectroscopic observation, and chemical analysis. Through the use of confocal Raman microscopy, this study addresses the effects of optical forces on the structure of unilamellar, dipalmitoylphosphatidylcholine (DPPC) vesicles, both optically trapped in solution and adhered to a coverslip. The energy and forces involved in optical trapping of lipid vesicles were derived in terms of the dielectric contrast between the phospholipid membrane and the surrounding solution; reflection forces at the membrane/water interface were found to be negligible. At optical powers of 9 mW and greater, unilamellar liposomes trapped in bulk solution experience a gradient force sufficiently strong to bend the vesicle membrane, so that a second bilayer from the same vesicle is drawn into the optical trap, with an energy of approximately 6 x 10(-13) erg. For vesicles adhered to a coverslip, the confocal probe can be scanned through the attached vesicle. Optical forces are insufficient to detach the bilayer that is adhered to the glass; however, the upper DPPC bilayer can be manipulated by the optical trap and the shape of the vesicle distorted from a spherical geometry. The effect of calcium ion on the flexibility of membrane bilayers was also tested; with 5 mM calcium ion in solution, the lipid bilayer of a surface-attached liposome is sufficiently rigid so that it cannot be distorted at moderate laser powers.     

Comparison of the effect of lipid A analog E5531 and the lipid A from Escherichia coli on phospholipid membrane properties

The effect of the lipid A analog E5531 on the phospholipid membrane was compared with that of the lipid A from Escherichia coli (EC). E5531 decreased the phase transition temperature of dipalmitoylphosphatidylcholine (DPPC) membrane and increased the fluidity and micropolarity. On the other hand, the effect of EC on the membrane was contradictory. These results suggested that the reason for the difference of biological effects of these two lipid A would be caused by the differences from the effect on the cell membranes.     

Dual‐Layer Superamphiphobic/Superhydrophobic‐Oleophilic Nanofibrous Membranes with Unidirectional Oil‐Transport Ability and Strengthened Oil–Water Separation Performance

Thin porous membranes with unidirectional oil‐transport capacity offer great opportunities for intelligent manipulation of oil fluids and development of advanced membrane technologies. However, directional oil‐transport membranes and their unique membrane properties have seldom been reported in research literature. Here, it is proven that a dual‐layer nanofibrous membrane comprising a layer of superamphiphobic nanofibers and a layer of superhydrophobic oleophilic nanofibers has an unexpected directional oil‐transport ability, but is highly superhydrophobic to liquid water. This novel fibrous membrane is prepared by a layered electrospinning technique using poly(vinylidene fluoride‐hexafluoropropylene) (PVDF‐HFP), PVDP‐HFP containing well‐dispersed FD‐POSS (fluorinated decyl polyhedral oligomeric silsesquioxanes), and FAS (fluorinated alkyl silane) as materials. The directional oil‐transport is selective only to oil fluids with a surface tension in the range of 23.8–34.0 mN m^–1. By using a mixture of diesel and water, it is further proven that this dual‐layer nanofibrous membrane has a higher diesel–water separation ability than the single‐layer nanofiber membranes. This novel nanofibrous membrane and the incredible oil‐transport ability may lead to the development of intelligent membrane materials and advanced oil–water separation technologies for diverse applications in daily life and industry.     

Thermodynamic and structural studies of mixed monolayers: Mutual mixing of DPPC and DPPG with DoTAP at the air–water interface

Phospholipid monomolecular films at the air–water interface are useful model membranes to understand miscibility among various components. Surface pressure (π)–area (A) isotherms of pure and mixed monolayers of dioleoyltrimethylammonium propane (DoTAP)–dipalmitoylphosphatidylcholine (DPPC) and DoTAP–dipalmitoyphosphatidylglycerol (DPPG) were constructed using a surface balance. DPPC and DPPG produced isotherms as expected and reported earlier. DoTAP, an unsaturated lipid, demonstrated a continuous π–A isotherm. Associative interactions were identified in DPPC–DoTAP mixtures compared to the pure components, while DPPG–DoTAP mixtures showed repulsive interaction up to an equimolar ratio. Compression moduli of the monolayers revealed that DPPC–DoTAP mixtures had increasing stability with increasing surface pressure, but addition of DoTAP to DPPG showed instability at low and intermediate concentrations. In both cases increased stability was returned at higher X_DoTAP values and surface pressures. Lipid monolayer film thickness values, determined on a gold coated glass substrate by surface plasmon resonance spectroscopy (SPR), indicated a systematic change in height profile for DPPC–DoTAP mixtures with increasing X_DoTAP. However, DPPG–DoTAP mixed monolayer systems demonstrated a biphasic response. The SPR data were in excellent agreement with our interpretation of the structure of solid supported lipid monolayers.     

Discriminating and imaging different phosphatidylcholine species within phase-separated model membranes by principal component analysis of TOF-secondary ion mass spectrometry images

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) enables chemically imaging the distributions of various lipid species in model membranes. However, discriminating the TOF-SIMS data of structurally similar lipids is very difficult because the high intensity, low mass fragment ions needed to achieve submicrometer lateral resolution are common to multiple lipid species. Here, we demonstrate that principal component analysis (PCA) can discriminate the TOF-SIMS spectra of four unlabeled saturated phosphatidylcholine species, 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC), 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), and 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) according to variations in the intensities of their low mass fragment ions (m/z ≤ 200). PCA of TOF-SIMS images of phase-separated DSPC/DLPC and DPPC/DLPC membranes enabled visualizing the distributions of each phosphatidylcholine species with higher contrast and specificity than that of individual TOF-SIMS ion images. Comparison of the principal component (PC) scores images to atomic force microscopy (AFM) images acquired at the same membrane location before TOF-SIMS analysis confirmed that the PC scores images reveal the phase-separated membrane domains. The lipid composition within these domains was identified by projection of their TOF-SIMS spectra onto PC models developed using pure lipid standards. This approach may enable the identification and chemical imaging of structurally similar lipid species within more complex membranes.     

Direct encapsulation of proteins into calcium silicate microparticles by water/oil/water interfacial reaction method and their responsive release behaviors

The direct encapsulations of proteins such as lysozyme, bovine serum albumin (BSA) and ovalbumin into calcium silicate microparticles were examined by interfacial reaction method using water/oil/water emulsion (W/O/W emulsion), which was effective for the preparations of silica and calcium carbonate microcapsules encapsulating biomacromolecules. Those proteins added to the sodium silicate solution of the W/O/W emulsion were successfully encapsulated into the microparticles, which were ascertained by diffuse reflectance ultraviolet (UV) and infrared spectra. The encapsulation efficiency of the proteins depended on the molecular weight of proteins, which were also observable in the protein encapsulations into silica and calcium carbonate microcapsules. No discharge of encapsulated proteins by simple washing with deionized water indicated the secure packing of proteins into calcium silicate matrix. Ethylenediamine-N,N,N′,N′-tetraacetic acid, tetrasodium salt (EDTA·4Na) effectively extracted calcium ions from the microparticles to serve as a trigger for the release of proteins, indicating that the elimination of calcium ion initiated the discharge of encapsulated proteins. The ion exchange between calcium and sodium ions also achieved the release of proteins into aqueous solutions. The release rate of proteins such as lysozyme and BSA increased with the concentration of sodium chloride less than 1 M. In diluted solutions, potassium chloride accelerated the protein release more than sodium chloride. These characteristic release behaviors must be applied to drug delivery systems that respond to the concentration of alkaline ions in body fluid.     

乳化炸药组分对体系界面张力的影响

采用吊片法分析乳化剂对碳质燃料油的表面张力以及乳化炸药组成材料对乳化炸药体系界面张力的影响。实验结果表明,油相材料的表面张力随乳化剂质量分数的增加而减小;在乳化炸药体系的水相中加入硝酸钠,可以降低体系的界面张力;油相材料的黏度增加,乳化炸药体系的界面张力也相应的增加;乳化剂质量分数大于1.0%时,乳化炸药体系的界面张力值趋向恒定。     

乳化炸药组分对体系界面张力的影响

采用吊片法分析乳化剂对碳质燃料油的表面张力以及乳化炸药组成材料对乳化炸药体系界面张力的影响。实验结果表明,油相材料的表面张力随乳化剂质量分数的增加而减小;在乳化炸药体系的水相中加入硝酸钠,可以降低体系的界面张力;油相材料的黏度增加,乳化炸药体系的界面张力也相应的增加;乳化剂质量分数大于1.0%时,乳化炸药体系的界面张力值趋向恒定。     

The Effect of Lipid A Analog E5531 on Membrane Properties of Dipalmitoylphosphatidylcholine

The effect of the lipid A analog E5531 on the phospholipid membrane was determined and compared with that of the lipid A from Escherichia coli (EC). E5531 decreased the phase transition temperature of dipalmitoylphosphatidylcholine (DPPC) membrane and increased the fluidity and permeability. On the other hand, EC increased the phase transition temperature and decreased the membrane fluidity and permeability. These results suggest that the reason for the difference of biological effects of E5531 and lipid A from EC would be caused by the differences from the effect on the cell membranes.     

DPPC/胆固醇混合LB膜的AFM研究

用LB膜技术将二棕榈酰磷脂酰胆碱(DPPC)和胆固醇的混合液转移到疏水云母上,并利用原子力显微镜(AFM)在空气中表征了LB膜的性质。结果表明,当C(DPPC)∶C(cho lestero l)=2.6∶1,膜压15mN/m时,能形成有缺陷的LB膜。并分析了这种缺陷LB膜的形成过程。此法制得的LB膜接近受损伤的肾上皮细胞膜,用于诱导晶体生长,从而建立受损伤的肾上皮细胞膜导致肾结石形成的化学模型。     

The effect of lipid A analog E5531 on membrane properties of dipalmitoylphosphatidylcholine

The effect of the lipid A analog E5531 on the phospholipid membrane was determined and compared with that of the lipid A from Escherichia coli (EC). E5531 decreased the phase transition temperature of dipalmitoylphosphatidylcholine (DPPC) membrane and increased the fluidity and permeability. On the other hand, EC increased the phase transition temperature and decreased the membrane fluidity and permeability. These results suggest that the reason for the difference of biological effects of E5531 and lipid A from EC would be caused by the differences from the effect on the cell membranes.     

Interfacial Tension Measurement With an Optofluidic Sensor

This paper reports a novel optofluidic sensor for measuring dynamic interfacial tensions. The field of optofluidics utilizes both microfluidics and micro-optics. Thus, our sensor consists of a microfluidic network and an optical detection system. The sensor is able to measure both surface tension and liquid/liquid interfacial tension. In the case of surface tension measurement, the liquid sample is introduced into a main channel, while air is injected through a T-junction. In the case of liquid/liquid interfacial tension measurement, a second immiscible liquid such as oil is introduced into a main channel, while the sample liquid is injected through the T-junction. The formation frequency of the microbubbles or microdroplets is a function of the interfacial tension between the two phases. This frequency can be measured easily by optical detection. Measurements were carried out for aqueous solutions with different concentrations of the ionic surfactant cetyl trimethyl ammonium bromide (CTAB). The actual interfacial tensions of these solutions were calibrated with a commercial tensiometer (FTA200, First Ten Angstrom). The measurement results show a clear relation between the interfacial tension and the formation frequency. Furthermore, our sensor can be used to identify the critical micelle concentration (CMC) of a surfactant. The sensor potentially allows the use of a minute amount of sample compared to the relatively large amount required for existing commercial systems     

C/Al复合材料界面反应动力学

本文通过对扩散控制C/Al界面反应的理论分析和试验测量,建立了模拟复合材料界面反应的动力学方程.理论分析求解的是一组反应扩散方程;实验测量界面反应层厚度用的是扫描俄歇微探针深度剖面分析方法.实验测量的结果很好地验证了理论分析所建立的界面反应动力学方程,并给出了所用样品界面反应的激活能.      

Atomic force microscopy studies of lateral phase separation in mixed monolayers of dipalmitoylphosphatidylcholine and dilauroylphosphatidylcholine

Atomic force microscopy imaging of dipalmitoylphosphatidylcholine (DPPC)/dilauroylphosphatidylcholine (DLPC) monolayers deposited onto alkanethiol modified-gold surfaces by the Langmuir–Schaefer technique was used to investigate domain formation in a binary system where phase separation arises from a difference in the alkyl chain lengths of the lipids. We have established how the condensed domain structure (shape and size) in DPPC/DLPC monolayers depends on the surface pressure and lipid composition. The mixed monolayers exhibit a positive deviation from an ideal mixing behavior at surface pressures of 32 mN/m. Lateral compression to pressures greater than the liquid-expanded-to-liquid-condensed (LE-to-LC) phase transition pressure of the mixed monolayer (8–16 mN/m) induces extensive separation into condensed DPPC-rich domains and a fluid DLPC matrix. The condensed structures observed at a few milliNeutons per meter above the LE-to-LC transition pressure resemble those reported for pure DPPC monolayers in the LE/LC co-existence region. At a bilayer equivalence pressure of 32 mN/m and 20 °C, condensed domains exist between x_DPPC 0.25 and 0.80, analogous to aqueous DPPC/DLPC dispersions. Compression from 32 to 40 mN/m results in either a striking distortion of the DPPC domain shape or a break-up of the microscopic DPPC domains into a network of nanoscopic islands (at higher DPPC mol fractions), possibly reflecting a critical mixing behavior. The results of this study provide a fundamental framework for understanding and controlling the formation of lateral domain structures in mixed phospholipid monolayers.