Langmuir单分子膜的动态稳定性:

应用KSV LB－5000型Langmuir膜天平的VISCOS模式,对硬脂酸和19,21－二炔二十二碳酸（DDA）单分子膜在有无亚相离子、不同目标膜坟、不同膜障振动频率和不同温度下的动态稳定性作了研究。实验表明,单分子膜的目标膜压越低,膜障交变振动的频率越低,单分子膜越稳定,亚相中加有金属正离子对单分子膜的动态稳定性也有利。     

制备条件对Langmuir－Blodgett膜中分子聚集态的影响

通过对不同制膜条件下样品的π－Ａ曲线及紫外－可见吸收光谱的测量，研究ＬＢ单分子层膜中半花菁衍生物（ｈｅｍｉｃｙａｎｉｎｅｄｅｒｉｖａｔｉｖｅ简称ＨＤ）分子的聚集状态及其形成机制。纯半花菁衍生物单分子层膜中分子以Ｈ聚集体的形式存在导致吸收峰的兰移及有效分子二阶非线性极化率β（基频波长λ＝１．０６４μｍ）的减小。实验表明聚集体的形成主要发生在压膜过程。提高压膜速度或降低压膜终极压力（拉膜压力）可显著减小分子的聚集程度，从而提高单分子层膜的光学非线性极化率。     

磷脂酰乙醇胺单分子膜的相变因素分析及原子力显微镜观测

通过π-A曲线(π:膜对浮片所施之力,A:单分子所占的面积)研究浓度、pH值、温度以及蔗糖对磷脂酰乙醇胺相变的影响.实验表明:(1)当浓度较高时,磷脂酰乙醇胺的π-A曲线随着浓度的增加重合性较好,平均分子面积和表面膜压有较好的对应.当浓度较低时,π-A曲线重合性较差,在低密度情况下,磷脂酰乙醇胺分子的排列不紧密,致使分子的随机运动对膜压的影响较大;(2)亚相处于较强的酸性或者碱性状态下均会使磷脂酰乙醇胺分子的相变变慢,pH值过高或过低都会对膜有较大的破坏作用;(3)当温度逐渐增大,而保持平均分子面积不变时,随着温度的增加,t-pa曲线(温度-膜压)逐渐由一条直线变成抛物线,这说明随着温度的增加磷脂酰乙醇胺凝聚膜会向液态扩张膜转变,即随着温度的增加相变延迟;(4)蔗糖对磷脂酰乙醇胺单分子膜有较强的稳定作用,且这种作用在生理条件下最为明显.用原子力显微镜直接观测了不同压力下转移至云母表面分子层的形貌特征,进一步解释了磷脂酰乙醇胺单分子膜相变的微观分子机制.     

光谱法研究入—4—（十六烷氧基）双酞菁镧的LB膜

测定了八－４－（十六烷氧基）双酞菁镧氯仿溶液在亚相水面上的π￣Ａ曲线，同时制备了它的ＬＢ膜。应用红外光谱及紫外－可见光谱法对其进行了研究。     

1－苄基－9－氢富勒烯－60LB多层膜的制备及其光学非线性性质

利用π－Ａ等温线、小角Ｘ射线衍射（ＳＡＸＤ）和光学测量方法研究了一种取代富勒烯（Ｃ６０－Ｂｅ）ＬＢ膜的结构特性。纯Ｃ６０－Ｂｅ分子以体相（ｂｕｌｋｐｈａｓｅ）的形式存在于气－液界面上。氮冠（醚）（ＮＣ）分子作为隔层材料，与Ｃ６０－Ｂｅ分子相混合可以制备性能优良的ＬＢ膜。π－Ａ、吸收和小角Ｘ光衍射测量表明：这种混合膜结构的改善是由于Ｃ６０－Ｂｅ分子镶嵌在ＮＣ分子的双脂链之间造成的。通过测量三次谐波产生（ＴＨＧ）可以推出Ｃ６０－Ｂｅ的三阶非线性系数χ（３）＝２．１×１０－１１ｅｓｕ。     

不对称冠醚酞菁LB膜制备过程中的亚相诱导作用

制备了单冠醚取代的不对称酞菁在不同亚相上的单层膜，并测定了π－Ａ曲线，将单层膜转移到氟化钙或单晶硅基片上，制备了多层膜，利用偏振紫外，光电子能谱和椭圆偏振对膜的结构进行了表征，证明了在膜中酞菁分子呈倾斜状态排列，分子平面和基片间的夹角受亚相中碱金属离子的影响，在纯不的表面，夹角最小，在１０＾－２ｍｏｌ／ＬＫＣｌ水溶液的表面，夹角最大，根据椭圆偏振法测定的膜的厚度可以推断，在膜中酞菁环上的疏水链呈伸     

十八胺单分子膜的研究

通过测定在纯水和CdCl2 溶液亚相上十八胺单分子膜的平衡、循环π～A等温线及其动态弹性 ,发现在亚相中加入Cd2 + 可以使膜的液态相凝聚性增强 ,固态相凝聚性减弱 .液态的单分子膜在两种亚相上有较好的可回复性 ,而在固态膜中则不然 .这可归因于在水面上十八胺分子间可形成氢键 ,而在CdCl2 水溶液亚相上的十八胺则与Cd2 + 发生配位 ,形成了多配位络合物 ,两种情况下十八胺分子在高膜压区都会发生稳定的聚集 .静、动态弹性的比较表明 ,膜障的振动不利于十八胺分子与Cd2 + 间的配位作用     

酞菁铜衍生物在酞菁酮—氧化铁纳米粒子交替LB膜中的分子取向

通过Langmuir-Blodett技术制备了酞菁酮－氧化铁纳米粒子交替LB膜,利用偏振紫外－可见光谱对酞菁铜衍生物在不同制膜条件下所制得的交替膜中的分子取向进行了研究。结果表明,在同一氧化铁溶胶亚相中,随着表面压的增大,或在相同的表面压下,随着亚相中氧化铁浓度的减小,酞菁铜分子在其复合LB膜中倾斜程度变大。     

花生酸与柿β—二酮络合物混合单分子膜的成膜特性

将β-二酮络合物(Ce(tmhd)4)的氯仿溶液与花生酸(AA)的氯仿溶液以不同摩尔比混合并铺展在纯水亚相上，得到其与AA的混合单分子膜．对混合单分子膜的成膜特性(π-A等温线和体系超额自由能)进行了探讨，发现混合单分子膜的超额自由能为负值，混合过程为热力学自发过程，且在配比为1：2时其绝对值最大，体系最稳定，并进一步讨论了混合单分子膜可能的凝聚态结构．在配比为1：2时，研究了混合单分子膜的静态弹性和动态弹性。     

Effects of Calcium Ions on Thermodynamic Properties of Mixed Bilirubin/Cholesterol Monolayers

通过?-A等温线研究了含钙离子浓度不同的水溶液亚相上胆红素/胆固醇混合单分子膜的性质．在此基础上,采用数学方法计算了不同亚相上单分子膜的平均单分子面积、崩溃压、表面压缩系数、超额单分子面积、混合自由能和超额自由能．结果表明,在钙离子溶液亚相上混合单分子膜的结构发生扩张,并且在界面上形成非理想混合单分子膜．与理想混合时相比,这种混合单分子膜在超额单分子面积上表现为明显的正偏差．在纯水亚相上,胆红素与胆固醇的摩尔比为3:2时混合单分子膜为热力学最稳定体系．但是在钙离子浓度逐渐增大的亚相中,这种摩尔比的混合单分子膜热力学稳定性被破坏,即混合单分子膜中的不同组分间自发混合能力下降,这是由于受到钙离子与胆红素和胆固醇之间配位作用的影响．此外,在钙离子溶液亚相中,在较低的表面压下制备出的混合膜具有更好的热力学稳定性．     

溴化N,N-二甲基二茂铁基十六烷基甲铵盐的合成、表征和性质研究

本文合成了新型两亲分子溴化N ,N 二甲基二茂铁基十六烷基甲铵盐 (FC1 6 AB) ,并利用UV Vis ,FTIR ,1 HNMR ,ESMS等手段进行表征。测量FC1 6 AB不同浓度的水溶液表面张力 ,表明其具有较好的表面活性。FC1 6 AB单分子膜的 π A曲线反映了FC1 6 AB成膜性能较好 ,亚相中抗衡离子的电荷和半径大小对FC1 6AB单分子膜有较大影响。     

Studies on behaviors of dipalmitoylposphatidylcholine and bilirubin in mixed monolayer at the air/water interface

Mixed monolayers of dipalmitoylposphatidylcholine (DPPC) and bilirubin (BR) were prepared on different subphases. The properties of DPPC/BR monolayer, such as collapse pressure (π_coll), limiting area per molecule (A_lim), surface compressibility modulus, free energy (ΔG_mix) and excess free energy (ΔG_ex), were investigated based on the analysis of the surface pressure-area isotherms on pure water. The results showed that DPPC and BR were miscible and formed non-ideal mixed monolayers at the air/water interface. With the molar fraction of BR (X_BR) increasing, the LE-LC coexistence region of DPPC monolayer was eliminated gradually. The DPPC/BR complex (M_D-B) of 1:2 stoichiometry formed as a result of the strong hydrogen bonds between the polar groups of DPPC and BR. The studies of effects of pH values and calcium ions in subphase on the DPPC/BR monolayers showed that the mixed monolayer became expanded on alkali aqueous solution and on 1 mmol/L CaCl₂ aqueous solution. The orientation of DPPC and BR at air/water interface was also discussed.     

水杨醛类希夫碱在LB膜上的光谱性能的研究

合成了两种末端碳锭长度不同的水杨醛类希夫碱N-十二烷基（2-羟基-5-硝基苯甲亚胺）和N-十六烷基（2-羟基-5-硝基苯甲亚胺），研究了它们在气-液界面上的成膜性能，并通过紫外、荧光、红外显微镜等光谱手段对它们在LB膜上的性能进行了表征。实验结果表明两种希夫碱分子在LB膜中都形成了J-聚体，末端碳链较长的希夫碱 成膜性能相对较好，并且在膜上也能光致发光，但希夫碱分子的LB膜存在一定的缺陷。     

Rigid rod adsorption including long-range dispersion interactions

The Caillé-Ågren analysis of rigid rod adsorption is extended by applying the van Kampen theory of condensation to include long-range dispersion interactions between the adsorbed rods. We discuss in greater detail the characteristics of the phase transition predicted by Caillé and Ågren between states having an isotropic and anisotropic distribution of rods adsorbed parallel to the surface. The maximum density range over which the anisotropic adsorbed phase is stable is determined as a function of the length-to-breadth ratio x of the rigid rods and the strength of the anisotropic dispersion energy. Critical surface adhesion and anisotropic dispersion energies necessary for anisotropic adsorption are also obtained as a function of x. In agreement with Caillé and Ågren the isotropic-anisotropic transition for rigid rod adsorption with attractive forces present is found to be second order. We also discuss the spreading pressure-density or area per molecule isotherms obtained for adsorbed rods having various values of x and surface adhesion and dispersion energies. Whenever feasible we compare our results with the spreading pressure isotherms obtained for monolayers of lyotropic molecules on either aqueous or mercury subphases and obtain qualitative agreement. In particular, the critical density and pressure associated with the two dimensional adsorbed gas-liquid condensation for rigid rods with x = 10 gives reasonable agreement with the critical constants observed by Hawkins and Benedek and Kim and Cannell for the corresponding condensation of pentadecanoic acid monolayers on neutral and acidified aqueous subphases. This agreement suggests that considerable dimerization of the pentadecanoic acid molecules may occur on aqueous surfaces.     

Influence of alcohol on mechanical and electrical properties of thin organic films

Stability of organic materials properties is essential for further applications and was intensely investigated in last few decades. The aim of this study is to detect the structural changes of dipalmitoyl-phosphatidylcholine (DPPC) monolayer as a model system of organic material under influence of alcohols solutions. As subphases of monolayers (Langmuir films), pure water, ethanol and methanol solutions were used. For detection of changes in charge states of the molecules as well as relation with structural and conformational changes, a contactless method employing Maxwell’s displacement currents (MDC) was used. In DPPC monolayer on the subphase of methanol-water, a gradual absorption of methanol molecules into the layer can appear. In DPPC monolayer on the subphase of ethanol-water adsorption of ethanol molecules on the layer can be observed. Influence of alcohols results in a significant change of mechanical and electrical properties as well as in the stability of thin films. Presented at 5-th International Conference Solid State Surfaces and Interfaces, November 19–24, 2006, Smolenice Castle, Slovakia     

Enhancement of abdominal organs on hepatic arterial phase: quantitative comparison between 1.5- and 3.0-T magnetic resonance imaging

Purpose

To compare the extent of enhancement of abdominal organs as shown on subphases of hepatic arterial phase quantitatively between 1.5- and 3.0-T MRI among patients with various abdominal conditions.

Materials and Methods

A total of 126 patients, of whom 68 were women (age range, 3–82 years; mean age, 48 years) and 58 were men (age range, 6–73 years; mean age, 50 years), were included in the study. Of 126 patients, 98 were scanned at 1.5 T and 28 were scanned at 3.0 T. The presence of one of three predefined subphases of hepatic arterial phase was determined on early post-gadolinium sequence in each patient by two reviewers in consensus. Extent of enhancement of the kidney, pancreas, spleen and liver on these subphases was determined quantitatively by measuring the signal intensities. Mann Whitney–Wilcoxon test was used to compare the contrast enhancement of organs on each subphase between 1.5- and 3.0-T MRI.

Results

The kidney, spleen, pancreas and liver demonstrated 1.79- to 2.45-, 1.65- to 1.97-, 1.66- to 1.8- and 1.1- to 2.02-fold higher enhancement on the subphases of hepatic arterial phase at 3.0 T compared to 1.5 T, respectively. The differences in contrast enhancement were significant for the kidney, pancreas and spleen on all subphases between 1.5 and 3.0 T.

Conclusion

The relative enhancement of the kidney, spleen and pancreas is consistently and significantly higher at 3.0 T than at 1.5 T in matched subphases of hepatic arterial enhancement.     

Ethanol and methanol induced changes in phospholipid monolayer

The main components of cell membranes are phospholipids and proteins. The aim of our study was to examine structural changes of dipalmitoyl-phosphatidylcholine (DPPC) monolayer as a simple model system of a cell membrane in different environments. Pure water, ethanol and methanol solutions were used as subphases of Langmuir films as a membrane models. For detection of changes in charge states of the molecules as well as relation with structural and conformational changes, a contactless method Maxwell's displacement currents (MDC) was used. Behaviour of DPPC molecules on two different subphases is substantialy different. In DPPC monolayer on the subphase of methanol-water, a gradual absorption (incorporation, penetration) of methanol molecules into the layer can appear. In DPPC monolayer on the subphase of ethanol-water adsorption of ethanol molecules on the layer can be observed. The membrane permeability might change. At both subphases (ethanol-water and methanol-water) the elasticity modulus of the monolayer decreases leading to the loss of membrane elasticity.     

Surface‐enhanced resonance Raman spectroscopic characterization of cytochrome c immobilized on 2‐mercaptoethanesulfonate monolayers on silver

Single‐component self‐assembled monolayers (SAMs) of mercaptoethanesulfonate (MES) on Ag surfaces were studied with surface‐enhanced resonance Raman scattering (SERRS) spectroscopy with a view to their application to immobilize (ferro)cytochrome c (cyt c). SERS studies revealed that MES molecules adopt primarily trans (T) conformation even at early stages of the SAM growth and over wide range of pH values. High accessibility of the negatively charged groups for (bio)molecules in solution makes single‐component MES SAMs suitable linkage monolayers for electrostatic attachment of cyt c, which was verified with SERRS. Cyt c was successfully anchored to MES‐coated Ag at natural (∼5), neutral, and isoelectric point (10.6) pH. At pH = 7.0 and 10.6, SERRS bands characteristic of native six‐coordinated low‐spin (6cLS) heme iron configuration were detected. Lack of buffering resulted in additional appearance of five‐coordinated high‐spin (5cHS) SERRS markers and the presence of bands indicating ferric ion. An electrostatic attraction between protein and SAM was confirmed to exclude the hydrophobic interactions involved in cyt c binding. Cyt c attached to MES SAM on Ag was found to be electroactive at neutral pH, and protein oxidation was assisted with reversible conversion of 6cLS to the non‐native 5cHS state. Alteration of heme orientation deduced from SERRS spectra upon change of redox state allowed us to propose the protein dynamics as the electron transfer rate‐limiting step. Copyright © 2010 John Wiley & Sons, Ltd.