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.     

Lanthanide ion induced formation of stripes domain structure in phospholipid Langmuir-Blodgett monolayer film observed by atomic force microscopy

Long-range ordered stripes domain structures were observed in Dipalmitoylphosphatidylcholine (DPPC) Langmuir-Blodgett monolayer film which was spread on the subphase of lanthanide ion (Eu³⁺) solution and transferred to a freshly cleaved mica substrate by vertical deposition. This novel phenomenon was discussed in terms of the competitive interaction of dipole-dipole and electrostatic interactions of the DPPC molecules combined with lanthanide ions with those DPPC molecules free of lanthanide ions.     

Ftir Studies on LB Film of Amphiphile with Schiff Base as Headgroup and Its Copper Complex

Two different ways to form monolayers and LB films (surface film and subphase film) of the complex have been used, where a novel amphiphile containing Schiff base as a headgroup was used as a ligand. the monolayer behavior at the air/water interface was characterized by π-A isotherms and two-dimensional molecular orientation of alkyl chains in LB films and thermal stability were measured by polarized and variable temperature FTIR transmission spectra, indicating that the LB film of the novel amphiphile and its copper(II) complex are very stable as well as stearic acid. Because incorporating the metal ion into the monolayer makes it more condensed, thermal stability of the LB film was enhanced. as can be compared from their structure and properties, subphase films are superior to surface films.     

Structure and properties of 1,4-benzenedimethanethiol films grown from solution on Au(1 1 1): An XPS and NEXAFS study

Core level photoemission and X-ray absorption at the carbon C 1s edge are applied to the study of chemisorption of 1,4-benzenedimethanethiol molecules on Au(1 1 1) and to investigate the effect of the solvent used to prepare the organic films. 1,4-Benzenedimethanethiol films were prepared in polar and non-polar solvents, i.e. ethanol, methanol and n-hexane. 1,4-Benzenedimethanethiol molecules are anchored to the substrate through a single S-Au bond; the molecules in the films tend to assume an upright orientation, the aromatic ring resulting tilted towards the direction perpendicular to the substrate plane. The films present an effective thickness corresponding to more than a single layer. Only small differences are observed among behaviours in different solvents. It is concluded that the final properties and conformation of the 1,4-benzenedimethanethiol films are largely determined by the reciprocal interactions between the molecules and with the substrate.     

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.     

一种可溶喹吖啶酮衍生物LB膜的光谱特性

采用表面压-分子面积(π~A)等温曲线、紫外-可见吸收谱和荧光光谱的方法研究了一种喹吖啶酮衍生物材料LB膜的制备及其光谱特性。实验表明,这种喹吖啶酮衍生物能够在水面上形成稳定的单分子膜,它与花生酸(AA)混合后不仅可以形成很好的单分子膜,而且可以较好的转移到固体基片上制备成LB膜多层膜。这种喹吖啶酮衍生物LB膜的紫外-可见吸收谱的吸收峰位较稀溶液发生了红移,这是由极性溶剂分子与其相互作用的结果。其溶液有很强的荧光效应,但LB膜没有荧光现象,原因是在LB膜中QAC16的浓度过高发生“自我猝息”而失光。它在溶液和LB膜中都是以单体的形式存在。     

Morphology of compressed dipalmitoyl phosphatidylcholine monolayers investigated by atomic force microscopy

The effectiveness of a substitute of natural lung surfactants on replacement therapy strongly depends on the stability of the monolayer of those substitute molecules. An atomic force microscope is utilized to investigate the microstructure of the films of the major components of natural lung surfactants, dipalmitoyl phosphatidylcholine—DPPC, which are transferred to mica substrates by the Langmuir-Blodgett film technique. A concave deformation structure was first observed for DPPC in solid phase. The depth of the concave domain was about 6 nm and was remarkably uniform. For a collapsed DPPC monolayer, the surface film consists of a granular convex multilayer structure and a disc-like concave structure. Dynamic cyclic compression-expansion experiments indicate that the formation of the concave domain is a reversible process while the process for convex multilayer formation is irreversible. This gives direct evidence that convex grain is the collapsed structure of DPPC monolayer and the concave shallow disc corresponds to the elastic deformation of a DPPC solid film. Results of atomic force microscopy indicate that the nucleation and growth model instead of the fracture model can better describe the collapse behavior of a DPPC monolayer.     

Structural Thermo‐ and Phototransformations of Oxaindane Spiropyrans Adsorbed on Silver Films

Using giant Raman scattering spectroscopy methods, we have studied the structure and also the thermo and phototransformations of dimethylphthalanspirobenzopyran (PhSBP) adsorbed on the surface of silver films. It is shown that on adsorption of PhSBP from ethanol solutions, on the surface of the silver films there are predominantly open forms of molecules which do not exhibit photochromic properties. It is established that cooling of the specimen to 77 K initiates thermoreversible reconstruction of the adsorption layer with formation of the aggregates of the PhSBP molecules. These reversible structural changes in frozen specimens are enhanced on exposure to the light of a visible range.     

Structure and magnetism of Fe mono‐ and multi‐layer systems as seen by conversion electron Mössbauer spectroscopy at atomic scale

The characteristic magnetic phenomena of ultrathin films are attributed to their reduced dimensionality and increased importance of the interfacial properties originated at their boundaries. The loss of nearest neighbor interactions at the interfaces, band hybridization, expansion or contraction of the atomic spacing occur, resulting in local changes of the energy band structure. Recent technical developments make it now possible to grow ultrathin films in a strictly layer‐by‐layer mode and to produce large areas of flat surfaces. Nevertheless, small structural perturbations in the local atomic configuration can still exist and result in significant changes of the global magnetic properties. Conversion Electron Mössbauer Spectroscopy (CEMS) determines the hyperfine interaction parameters which are sensitive to the arrangement at the atomic scale. In particular, depth selectivity at a monolayer level has been achieved in Fe films with one atomic layer replaced by the Mössbauer isotope ⁵⁷Fe. This contribution reviews the experimental work on magnetic phenomena of bcc, fcc and hcp Fe ultrathin films (including monolayer and multilayer structures), epitaxially grown by condensation from molecular beam under ultrahigh vacuum conditions. Since the structural and magnetic information can be achieved by using one method only, Mössbauer spectroscopy is pointed out as being an extremely effective and convenient tool for such purposes.     

醇类抑制剂对甲烷水合物形成的影响

在本工作中,甲烷水合物的生长动力学是通过甲醇、乙醇、乙二醇三种不同醇类抑制剂存在下的分子动力学模拟研究的.模拟结果发现,三种醇类都可作为甲烷水合物的抑制剂,醇类分子中的亲水性羟基极大地破坏了水合物笼的结构,并且羟基可以与局部的液态水分子形成氢键,从而增加了形成水合物笼型结构的难度,导致甲烷水合物的生长速率降低.对于甲醇分子,甲醇分子的亲水性羟基与水分子形成氢键从而破坏了水分子结构,而亲油性甲基对周围的水分子具有簇效应,两者都会降低水合物生长速率;对于乙二醇和乙醇分子,它们只含有羟基,特别是乙二醇分子含有两个羟基,其对H₂O分子有很强的吸附作用,导致水合物生长速率降低.在抑制效果方面,甲醇分子最优,乙二醇稍微优于乙醇.     

Structural evolution at the initial growth stage of perylene on Au(1 1 1)

We report on the structural evolution at the initial growth stage of perylene thin films on Au(1 1 1) surface. Scanning tunneling microscopy and spectroscopy have been employed to investigate the structural and electronic properties at 78 K. Rapid molecular diffusion was observed at low submonolayer coverage. Molecules form an ordered structure at monolayer coverage. For the second layer, impinging molecules nucleate into molecular islands with an ordered intermediate structure.     

Decomposition pathways of C1C4 alcohols adsorbed on platinum (111)

The adsorption and decomposition of methanol, ethanol, propan-1-ol, propan-2-ol and butan-1-ol has been studied on clean, and oxygen pre-covered Pt(111) surfaces. Temperature Programmed Reaction Spectroscopy (TPRS), Surface Potential Measurements (ΔV), UPS and XPS were used to characterise the adsorbed layer as a function of temperature. Each alcohol adsorbed into two states, a monolayer phase and a multilayer phase which were distinguishable by TPRS and Spectroscopy measurements. The monolayer alcohol adsorption heats increased sequentially from methanol to n-butanol (11.5–15 kcal mole^?1). On the clean surface, less than 10% of the adsorbed monolayer dissociated, with 90% of the alcohol desorbing intact. Two competing dissociative pathways were observed: complete dissociation to adsorbed CO, H and C, and with propan-1-ol and butan-1-ol, scission of the CC bond nearest the CO group to form adsorbed CO, H and ethylidyne and propylidyne species respectively. The latter reaction probability was constant at 30% for n-propanol and n-butanol. In all cases the final desorption products were the parent alcohol, CO and H₂ with carbon remaining on the surface for the higher alcohols. Atomic oxygen removed hydrogen from the alcohols as water but did not change the final reaction products.     

Observation of phase separation of phospholipids in mixed monolayer Langmuir-Blodgett films by atomic force microscopy

We report here the first AFM studies of phase-separated monolayer Langmuir-Blodgett films composed of a mixture of L-α-dipalmitoylphosphocholine (DPPC) and peptide bond bridged dl-α-phenylalanine-tetraphenylporphyrin (PTPP) under different surface pressures. The shapes of DPPC domains as well as microstructures within domains were also directly observed by AFM.     

Investigation of the sorption properties of thin Ge–S–AgI films deposited on cantilever-based gas sensor

Thin amorphous Ge–S–AgI films were thermally evaporated on cantilever sensors and their sorption properties were investigated upon exposure to volatile analytes, such as water, ethanol, acetone, and ammonia vapours. The films were smooth and uniform in thickness as revealed by atomic force and scanning electron microscopies. The exposure to the analytes resulted in a change of the resonance frequency of the cantilever. Initially, the largest dynamic responses (frequency shifts) were observed towards acetone, i.e. the cantilever acted as a resonant microbalance. When the sensor was exposed to ammonia, its molecules were chemisorbed on the surface of the sensitive layer. This surface modification increased the sensor sensitivity towards water molecules by the creation of new interaction sites. PACS 81.05.-t; 85.85.+j; 07.07.Df     

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     

Domain structures of phospholipid monolayer Langmuir-Blodgett films determined by atomic force microscopy

Atomic Force Microscopy (AFM) has been used to show the formation of solid-phase domains from fluid-phase domains on compression of DiPalmitoyl-PhosphatidylCholine (DPPC) monolayer Langmuir-Blodgett (LB) films. The chiral structures on the solid substrates were observed for the first time. By applying the friction force technique, we were able to distinguish the different regions of LB films according to their elastic properties. The influence of rates of compression on the domain shape as well as the microstructure within the domain were also studied.     

Preparation and probe analysis of Langmuir–Blodgett films with metal-containing dendritic and cluster structures

We aim to reveal the influence of?pH values of the working solution on spatial arrangement of metal-containing inclusions in the monolayer coatings prepared by Langmuir?CBlodgett (LB) technology and transferred to solid substrates with consequent modification of surface electrical properties. Consequently, films with inclusions in the form of dendrites and cluster shapes have been obtained. Submicron and micron lead-containing formations in Langmuir?CBlodgett films have been characterized by using the atomic force microscopy, Kelvin probe microscopy, and scanning electron microscopy methods. The results show that increasing?pH value of the subphase has caused the significant changes in the shape and composition of the inclusions in Langmuir?CBlodgett films. The synthesized inclusions on the solid substrate surface resulted in formation of the regions with the local electric fields and, as consequence, to significant modification of the structure and electrical properties. The location and length of the regions with surface potential disturbance depend on the shape of inclusions, and consequently, on?pH value of the subphase used in LB technology.     

Synthesis of graphene from naphthalene molecules on the surface of a Langmuir monolayer

This paper considers some approaches to the technology of the synthesis of a graphene monolayer at a phase interface. A surfactant monolayer on an aqueous subphase is proposed as the substrate for graphene synthesis. A monolayer is formed by the Langmuir–Blodgett method. Simple polyaromatic molecules, in particular, naphthalene, are considered as the basic substance for the synthesis of graphene. Arachidic acid is used as the basic surfactant molecule. To confirm the possibility of synthesizing graphene by the mentioned method, both experimental and theoretical studies are performed. In the course of experiemnts, it is shown that naphthalene molecules are pressed into the space above arachidic acid molecules upon the compression of monolayer of arachidic acid–naphthalene mixtures (such an assumption is made due to the characteristic value of the surface areas attributed to different phases of the monolayer and also to its characteristic parameters). The formation of a layer of naphthalene molecules on the surface of a monolayer is modeled by the molecular dynamics method (Amber potential). Different variants of the initial distribution of molecules are considered.     

The effects of solvent nature on spray-deposited ZnO thin film prepared from Zn (CH3COO)2, 2H2O

Transparent conducting zinc oxide was deposited on glass substrate by ultrasonic spray method. The ZnO samples with concentration of 0.1 M were deposited at 300, 350 and 400 °C with 2 min of deposition time. The effects of substrate temperature, ethanol and methanol solution on the structural, electrical and optical properties were examined. The DRX analyses indicated that ZnO films have polycrystalline nature and hexagonal wurtzite structure with (1 0 0) and (0 0 2) preferential orientation corresponding to ZnO films resulting from methanol and ethanol, respectively. The crystallinity of the thin films improved with ethanol solution. All films exhibit an average optical transparency about 80%, in the visible range. The band gap energy of ZnO films obtained with methanol solution higher than of ethanol solution for all the films. The electrical resistivity decrease with ZnO obtained from ethanol indicated; due to the maximum crystallite size retched at this point.     

硬脂酸单分子膜上电沉积Ag膜的研究

通过电沉积方法 ,以气 /液界面上形成的硬脂酸单分子膜为模板诱导沉积金属银膜 .考察了镀液 pH值、单分子膜表面压及沉积电位对银膜形貌及结构的影响 .实验发现 ,酸性镀液的气 /液界面上形成的单分子膜不能诱导沉积银 ,而在中性和碱性镀液的气 /液界面上可以诱导银膜的生长 .当单分子膜处于液态或固态时 ,气 /液界面有银膜形成 ;液态单分子膜上的银膜生长速度较快 ,且银膜的结构一致 .随着电极电位的升高 ,银膜沉积的速度加快 ,呈环状向外生长的圆形银膜逐渐变得不规则 .将不同实验条件下的银膜转移出来 ,采用扫描电镜 (SEM )、透射电镜 (TEM )对银膜的结构与形貌进行了表征 .研究表明 ,银首先在单分子膜上异相成核 ,由八面体构型逐渐发展成星型 ,最终在气 /液界面形成具有松枝状微观结构的光亮银膜 .