钙离子和镁离子浓度变化对磷脂酰乙醇胺-磷脂酰甘油双分子层膜的影响（英文）

钙离子和镁离子是生物细胞中重要的二价阳离子,对生物膜结构保持和功能行使发挥重要作用。但至今,对两种阳离子在不同浓度下与大肠杆菌内膜相互作用的认识仍存在局限。本文采用动态光散射(DLS)、zeta电势实验、全原子分子动力学模拟(AA-MD),定量研究了不同浓度的钙离子和镁离子对混合磷脂双分子层膜(1-棕榈酰基-2-油酰基-sn-丙三基-3-磷酸乙醇胺(POPE):1-棕榈酰基-2-油酰基-sn-丙三基-3-磷酸甘油(POPG)的摩尔比为3:1)模拟的大肠杆菌内膜的影响。DLS结果表明,在0和1 mmol·L~(-1)钙离子或镁离子溶液中,POPE/POPG脂质体为均匀的单分散体系。当两种离子浓度分别提高到5–100 mmol·L~(-1)范围时,单室脂质体间发生脂分子聚集或脂质体融合事件。Zeta电势数据表明,钙离子或镁离子对电负性的POPE/POPG脂质体均有电荷反转效果。AA-MD模拟计算结果表明,当模拟时间超过100 ns时,各浓度的钙离子稳定地吸附在磷脂双分子层膜上,而镁离子动态地吸附/解吸附于磷脂膜,这些结果与DLS和zeta电势实验基本吻合。同时,通过计算径向分布函数,分析了0、5、100 mmol·L~(-1)浓度溶液中POPE和POPG的磷酸、羰基和羟基基团氧原子的第一配位壳层中的钙离子或镁离子的平均配位数目,结果表明两种离子主要结合在POPE和POPG电负性的磷酸基团上,因此可以解释DLS实验中钙离子或镁离子对POPE/POPG脂质体的电荷反转现象。另外,随着离子浓度的增高,钙离子减小了磷脂双分子层膜的单个磷脂面积,同时使膜的厚度增大,而镁离子对膜的两种参数影响较小。同时,相同浓度条件下两种离子对膜中磷脂分子的取向影响不同。这些模拟结果可在原子水平上解释DLS和zeta电势实验中钙离子和镁离子对POPE/POPG脂质体的不同影响。本文的实验和分子动力学模拟结果可以解释一些与二价阳离子调控相关的生物学过程,例如,膜融合。     

超薄双层膜——“生物分子电子器件”(BED)的一个实验途径

引言 自从双分子(双层)厚度的、能分隔开两个水溶液的超薄类脂膜问世二十多年来,人们对它的兴趣与日俱增。这种薄类脂膜具有两个界面,其厚度小于10nm,在可见光下,这种膜看起来是“黑”的。     

双层脂和膜生物能量学中的826-氧化还原反应

本文对超薄人造双分子层膜(BLM)和叶绿体及线粒体生物膜中的电子过程进行了研究,总结了由伏安技术所得的近期实验。还讨论了基础电化学在膜研究中的应用,尤其对Eyring方程、Butler-Volmer方程和Tafel方程,以及按照膜孔电积作用在膜中的电子过程的起源进行了论述。讨论了在缺少双层脂的情况下确定氧化还原蛋白组分的标准电位(U′_0,对双层脂膜中有关的电子转移和生物氧化还原提出了设想。     

盐浓度及磷脂分子结构对多组分带电膜弯曲刚性的影响

磷脂膜弯曲刚性模量很难直接测量, 本实验用循环冻融法制备尺寸大小与膜弯曲刚性相关的熵稳定单层囊泡. 粒度仪测量发现, 囊泡尺寸随盐浓度增加呈现先剧烈减小然后缓慢增加的分段变化规律. 但当组分中含有头部带电同时尾链带有不饱和键的二油酰磷脂酰甘油酯时, 囊泡尺寸却在较大的盐浓度范围内不出现回升. 囊泡膜的负Zeta-电势绝对值均表现为先急剧减小然后趋于平稳的变化规律, 数值大小只与带电组分的含量有关. 而对直接水合法制备的多层囊泡的统计发现, 囊泡尺寸随盐浓度增加急剧减小, 随后趋于稳定值, 均不随分子组合变化而回升. 结果表明在不同的盐浓度范围里, 主导磷脂膜弯曲刚性模量的因素不同. 低盐浓度的体系, 静电屏蔽效应为主导因素; 高盐浓度的体系, 膜双电层中反离子的分布起主导作用. 磷脂分子头部与尾部的不同结构组合会影响膜双电层, 使膜的弯曲刚性不同. 多层囊泡体系中, 高盐浓度下膜的热涨落掩盖了分子结构及双电层分布差异对膜弯曲刚性的影响.     

槲皮素修饰的双层脂膜的伏安研究

槲皮素修饰的从层脂膜作为研究抗病毒药物的一种模型体系,用循环伏安法测定了槲皮素在脂膜界面上的氧化还原性质和配位性质。在电位扫描过程中,微量铜离子能催化槲皮素的氧化,当双层脂膜的两侧存在着合适的氧化还原偶时,就会产生跨膜的电子传递。     

用液相二次离子质谱技术探测Melittin与磷脂膜的相互作用

利用液相二次离子质谱技术(LSIMS)结合特异性蛋白酶降解研究了膜结合Melittin的“抛锚”状态.结果显示,Melittin(蜂毒素)分子在磷脂膜上为平躺α-螺旋结构,其螺旋中含Lys_7,Lys_(21),Arg_(22)的一侧朝向磷脂膜的外部.这一发现对蜂毒素插膜机制的研究具有十分重要的意义.结果还表明,质谱技术与专一性蛋白水解酶的结合为膜插入机制的研究提供了一个崭新的、行之有效的方法.     

表面修饰富勒烯的聚酰胺-胺树枝状分子与生物膜的相互作用研究

采用粗粒化的分子动力学模拟,研究了末端修饰富勒烯(C60)的聚酰胺-胺(PAMAM)树枝状分子在水溶液中的结构变化以及其与磷脂膜相互作用行为.发现修饰后的PAMAM分子大小随嫁接数目的增多而减小,而形状变化并不明显,分子仍是近球形结构;同时发现C60分子因疏水作用聚集在一起.与膜作用后,因C60分子插入到双层膜内,导致分子由球形稍微向椭球形改变,分子大小也稍微增大.同时发现PAMAM分子紧紧分布在磷脂膜表面,局域膜厚度变小.     

鞘氨醇与DPPC, DPPE单层膜的热力学特性及形态观察

鞘氨醇(sphingosine)是生物体内合成鞘脂的母体化合物, 是生物膜中的重要组分之一. 通过分析表面压力和平均分子面积(π-A)等温线数据分别研究了鞘氨醇与二棕榈酰基磷脂酰胆碱(DPPC)和二棕榈酰基磷脂酰乙醇胺(DPPE)二元组分单层膜的热力学特性, 并在恒定膜压下制备不同摩尔比例的混合脂膜用原子力显微镜进行观测. 实验结果表明: (1)鞘氨醇与DPPC组成的系统中, XD-Sph＝0.2, 0.4, 0.6时, 过量分子面积与过量吉布斯自由能在所研究的表面压力下表现为负值, 而当XD-Sph＝0.8时, 表现为正值; (2)鞘氨醇与DPPE组成的系统中, 当表面压力 π＜25 mN•m－1时, 过量分子面积与过量吉布斯自由能在所研究的组分比例下表现为负值, 当π≥25 mN•m－1时为正值. 混合单层膜的分子面积与表面吉布斯自由能决定了分子间的相互作用, 当为负值时分子间相互作用表现为吸引力, 出现凝聚现象; 为正值时分子间相互作用表现为排斥力, 促使单层膜出现相分离现象. 过量吉布斯自由能值越小, 单层膜的热稳定性越高. 弹性系数曲线分析和AFM图片观测进一步验证了理论分析的结果.     

自组装ITO/双层磷脂膜的制备及其光电行为研究

在ITO(Indium-tin-oxide)导电玻璃电极上制备上自组装双层磷脂膜和经C60修饰的双层磷脂膜,研究了这种自组装双层磷脂膜的光电行为,考察了偏压、溶液中的给体和受体的浓度对自组装膜光电流强度的影响,讨论了C60分子对光电子跨膜传递过程的促进作用。     

充蜡石墨支撑的季铵离子/己二酸混合双层膜上钙离子诱发的离子通道行为

以充蜡石墨电极作为新型支撑体,成功制备了一种季铵离子为内层（包括四丁 基铵TBA,十六烷基三甲基铵CTrMA）,己二酸（HDA）为外层的新型自组装混合双 层膜,以循环伏安和电化学交流阻抗方法研究了膜的离子通道行为。该膜能够接受 Ca~(2+)的刺激作用而打开[Fe(CN)_6]~(3-/4-)电极氧化还原的离子通道,撤走该 刺激离子则通道关闭。提出了混合双层膜的结构和离子通道作用的模型,指出外层 膜HDA分子可能具有V型和W型两种结构。     

膜片电极支撑自组装双层脂膜中短杆菌肽离子通道的形成

通过一个两步程序在膜片电极尖端形成自组装双层脂膜：（1）膜片电极尖端沾取成膜液；（2）将吸附成膜液的尖端浸入电解液中，排除尖端多余的成膜液，通过电学方法监测双层脂膜的形成。将短杆菌肽通道蛋白分散在成膜液和电解质溶液中，在制备膜片电极支撑双层脂膜过程中，短杆菌肽重组到双层脂膜中形成离子通道，对通道的一般特性进行了研究，并观察到通道开放和关闭的现象。     

Ionic Diffusion Through Unblended PVC Membranes

Abstract

This work deals with the study of the diffusion of Cl^? ion through pure unblended polyvinylchloride (PVC) membranes of different thickness. Several PVC -tetrahydrofuran ratios and also different internal diameter glass disks have been used to change the thickness of the membrane. A chloride ion selective electrode also constructed in the laboratory is used as the detector. The electrode behaviour was studied by running up a calibration graph prior to membrane positioning. A mean slope of 57 ±1 mV/log.C at 28.0 ± 0.5 °C was obtained and the range of potential values were then known. The detector was very well washed and immediately a membrane was placed directly on its surface and assembled to a rotating disk electrode in order to get a diffusion cell. The receiving compartment in this system has a negligible volume. Therefore, the response of the chloride ion selective electrode is directly proportional to the flux of material through the membrane rather than to the receiving compartment concentration. An almost linear relationship between the Cl^? ion concentration in the range 0.0010 – 0.10 M and its flux through the unblended PVC membrane was found. The chloride ion flux through the PVC membrane in solutions with the ion strength adjusted to 0.1 M was twice to that value obtained without ion strength adjustor (ISA) in the solution. Average rate transport in the range 3.5?10^?7 to 9.6?10^?7 mol/s Cl^? was found at a rotation speed of 1280 rpm.     

Ion-selective Membranes Prepared Upon Layer-by-Layer Assembly of Azamacrocycles and Polyelectrolytes

Summary : Recent studies on ion transport across multilayered membranes of azamacrocycles and polyelectrolytes are reviewed. Membranes were built up on porous PAN/PET supports using electrostatic layer-by-layer assembly. Two types of separation membranes were prepared, type I consisting of protonated hexaazacyclooctadecane and polyvinylsulfate, and type II of hexaazacyclo-octadecane hexaacetic acid and protonated polyvinylamine. Ion transport was studied under dialysis, nanofiltration and reverse osmosis conditions. Type I membranes were suitable for efficient separation of mono- and divalent anions, whereas type II membranes were suited for separation of mono- from di- and trivalent cations.     

Functional Tethered Bilayer Lipid Membranes on Aluminum Oxide

Tethered bilayer lipid membranes are established as well‐suited model membrane systems adaptable to different surfaces, for example, gold and silicon. These solid supported membranes are highly flexible in their tethering and lipid parts and can thus be optimized for functional incorporation of membrane proteins. The excellent sealing properties of the tethered membranes allow incorporated ion‐channel proteins to be investigated. Preparation of ultrasmooth aluminum oxide by sputtering and synthesis of new tethering lipids with phosphonic acid anchor groups enable formation of an electrically sealing membrane on this surface. This process is monitored by electrochemical impedance spectroscopy and by surface plasmon resonance spectroscopy. High sealing performance of the membrane and functional incorporation of the ion carrier valinomycin are demonstrated.     

重离子径迹模板法合成银纳米线

聚碳酸脂(PC)膜被高能重离子辐照后沿入射离子路径产生潜径迹, 把带有潜径迹的膜经紫外光敏化后置于NaOH 溶液中进行蚀刻, 通过选择蚀刻条件, 在PC 膜内得到直径从100 到500 nm 导通的核径迹孔. 以带有核径迹孔的PC 膜为模板, 用电化学沉积法制备出不同直径的银纳米线. 在特定的实验条件下(沉积电压25mV、电流密度1-2 mA·cm-2、温度50 益和电解液为0.1 mol·L-1的AgNO3溶液), 获得了沿[111]方向择优取向生长的具有单晶结构的银纳米线. 利用扫描电子显微镜(SEM)、X射线衍射(XRD)、透射电子显微镜(TEM)及选区电子衍射(SAED)等手段对银纳米线的形貌和晶体结构特征进行了表征.     

Electroviscous Effects in Ceramic Nanofiltration Membranes

Membrane permeability and salt rejection of a γ‐alumina nanofiltration membrane were studied and modeled for different salt solutions. Salt rejection was predicted by using the Donnan‐steric pore model, in which the extended Nernst–Planck equation was applied to predict ion transport through the pores. The solvent flux was modeled by using the Hagen–Poiseuille equation by introducing electroviscosity instead of bulk viscosity. γ‐Alumina particles were used for ζ‐potential measurements. The ζ‐potential measurements show that monovalent ions did not adsorb on the γ‐alumina surface, whereas divalent ions were highly adsorbed. Thus, for divalent ions, the model was modified, owing to pore shrinkage caused by ion adsorption. The ζ‐potential lowered the membrane permeability, especially for membranes with a pore radius lower than 3 nm, a ζ‐potential higher than 20 mV, and an ionic strength lower than 0.01 m . The rejection model showed that, for a pore radius lower than 3 nm and for solutions with ionic strengths lower than 0.01 m , there is an optimum ζ‐potential for rejection, because of the concurrent effects of electromigration and convection. Hence, the model can be used as a prediction tool to optimize membrane perm‐selectivity by designing a specific pore size and surface charge for application at specific ionic strengths and pH levels.     

Theory of Ion Transport in Electrochemically Switchable Nanoporous Metallized Membranes

A physicomathematical model of ion transport through a synthetic electrochemically switchable membrane with nanometric metal‐plated pores is presented. Due to the extremely small size of the cylindrical pores, electrical double layers formed inside overlap, and thus, strong electrostatic fields whose intensities vary across the cross‐sections of the nanopores are created. Based on the proposed model a relationship between the relative electrostatic energies experienced by ions in the nanopores and the potential applied to the membrane is established. This allows the prediction of transference numbers and explains quantitatively the ion‐transport switching capability of such synthetic membranes. The predictions of this model agree satisfactorily with previous experimental data obtained for this type of devices by Martin and co‐workers.     

Microhole-voltammograms Controlled by Solution Reservoir at Cationic and Anionic Ion Exchange Membranes

Microhole-voltammetry in which ions pass through a hole by electric migration exhibits rectified current-voltage curves. The rectification ratio, being of the high conductance to the low one, seems to depend on properties of ion exchange membranes. Our experiments at a cationic and an anionic membrane showed that the ratios for both the membranes were similar in spite of large difference in ionic capacities. The ratio was controlled by geometry of the reservoir of the solution rather than hole geometry and properties of membranes. Our model was composed of resistances of the hole, the membranes and the reservoir in series.     

Inorganic Membranes for Hydrogen Separation

Hydrogen, one of the most promising energy carriers for the future, is currently produced mainly by natural gas reforming or coal gasification, where mixtures containing H₂, CO₂ and contaminants like CO, H₂S and CH₄ are obtained. Among other methods, membrane technology has received special attention due to its potential efficiency for hydrogen separation, simplicity of operation, low energy consumption, and because it is environmentally friendly. For this application, the inorganic membranes can be essentially divided into five main families: metallic and proton conducting (dense phases), and silica, zeolite and carbon molecular sieve (porous solids). Over the past 20 years, palladium-based membranes have been the most studied and implemented at industrial level; however, recent advances in other membrane types have received a great deal of attention. This article critically reviews more than 520 publications, highlighting the latest research developments on inorganic membranes for the recovery and purification of hydrogen, with emphasis on their structural characteristics, synthesis, commercial application, drawbacks and challenges. Furthermore, a large compilation of data is provided in Supplementary Material divided according to membrane type.     

Polymeric Microfiltration Membranes Modification by Supercritical Solvent Impregnation—Potential Application in Open Surgical Wound Ventilation

This study investigated supercritical solvent impregnation of polyamide microfiltration membranes with carvacrol and the potential application of the modified membranes in ventilation of open surgical wounds. The impregnation process was conducted in batch mode at a temperature of 40 °C under pressures of 10, 15, and 20 MPa for contact times from 1 to 6 h. FTIR was applied to confirm the presence of carvacrol on the membrane surface. In the next step, the impact of the modification on the membrane structure was studied using scanning electron and ion beam microscopy and cross-filtration tests. Further, the release of carvacrol in carbon dioxide was determined, and finally, an open thoracic cavity model was applied to evaluate the efficiency of carvacrol-loaded membranes in contamination prevention. Carvacrol loadings of up to 43 wt.% were obtained under the selected operating conditions. The swelling effect was detectable. However, its impact on membrane functionality was minor. An average of 18.3 µg of carvacrol was released from membranes per liter of carbon dioxide for the flow of interest. Membranes with 30–34 wt.% carvacrol were efficient in the open thoracic cavity model applied, reducing the contamination levels by 27% compared to insufflation with standard membranes.