Stabilization of Langmuir monolayer of hydrophobic thiocholesterol molecules

The self-assembled monolayer of the thiocholesterol (TCh) exhibits interesting properties that can be used for various technological applications. TCh is predominantly a hydrophobic molecule, and it does not spread at the air–water interface to form a stable Langmuir monolayer. We have stabilized the TCh molecules in the cholesterol (Ch) monolayer. We find the mixed monolayer to be stable upto 0.75 mole fraction of TCh in Ch. The mixed monolayer shows an initial and a final collapse. On compressing the monolayer beyond the initial collapse, the TCh molecules squeeze out irreversibly from the mixed monolayer phase. The calculation of excess area per molecule for the TCh and Ch mixed monolayer system indicates an attractive interaction between the component molecules. Interestingly, the elasticity of the Ch monolayer reduces to less than half, and the monolayer becomes more fluidic due to the presence of even very minute quantity (5%) of TCh.     

Commensurate-incommensurate transition of 4He adsorbed on a single C60 molecule

Path-integral Monte Carlo calculations have been performed to study (4)He adsorption on a single C(60) molecule. Helium corrugations on the fullerene molecular surface are incorporated with the (4)He-C(60) interaction described by the sum of all (4)He-C interatomic pair potentials. Radial density distributions show a layer-by-layer growth of (4)He with the first adlayer being located at a distance of ~6.3 ? from the center of the C(60) molecule. The monolayer shows different quantum states as the number of (4)He adatoms N varies. For N = 32, we find a commensurate solid, with each of the 32 adsorption sites on the molecular surface being occupied by a single (4)He atom. Various domain-wall structures are observed as more (4)He atoms are added and the first layer crystallizes into an incommensurate solid when it is completely filled. This commensurate-incommensurate transition of the helium monolayer is found to be accompanied by re-entrant superfluid response at a low temperature of 0.31 K with the superfluidity being totally quenched at N = 32, 44, and 48. Finally, the different quantum states observed in the helium monolayer around C(60) are compared with phase diagrams proposed for the corresponding layer on a graphite surface.     

花生酸与铈β-二酮络合物混合单分子膜的成膜特性

将铈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.     

Nonideal mixing of 16-(9-anthroyloxy) palmitic acid and fatty acid in monolayer

The surface pressure-molecular area curve of the mixed monolayer of 16-(9-anthroyloxy) palmitic acid (16AP) and fatty acid (palmitic or stearic acids) showed various kink points which indicated the phase transitions of the monolayer. On the basis of the surface phase rule, the phase diagrams of the mixed monolayer were elucidated. The bifunctional molecule, 16AP, takes two orientations in a monolayer state, that is, horizontal and vertical ones. Horizontally oriented 16AP and vertically oriented fatty acid form a mixed monolayer but this exhibits deviation from the ideal mixing, which was interpreted in terms of the surface regular solution theory. On the other hand, the 16AP molecule in the vertical state was found to be immiscible with the fatty acid molecule in a monolayer de spite both molecules being vertical to the surface and parallel to each other. This was caused by the participation of the 9-anthroyloxy moiety of 16AP in the interaction of 16AP and fatty acid in the hydrophobic region of the monolayer.     

A nanotumbleweed: breaking away a covalently tethered polymer molecule by noncovalent interactions

A covalently tethered polymer molecule can spontaneously break away from the surface when polymer/surface interaction is sufficiently unfavorable. This is demonstrated in surface-initiated polymerization of a hydrophilic polymer, hyperbranched polyglycidol, from minority surface sites embedded in a hydrophobic self-assembled monolayer. As each hyperbranched polyglycidol molecule grows larger, it encounters more unfavorable interaction with the hydrophobic surface, and this leads to spontaneous bond rupture and desorption. This finding challenges the traditional view on noncovalent interaction of macromolecules with the local environment at interfaces and has broad implications for the understanding, design, synthesis, and applications of surface-tethered macromolecules.     

Grafting and growing mechanisms of polymerised organic films onto metallic surfaces

The build up of a homogeneous polyacrylonitrile film laid down by electropolymerisation on a metallic surface begins by the chemisorption of a monomer monolayer. As the growth of the conducing film proceeds (conduction by hopping) the number of electrons is constant. The electronic properties of the substrate and monolayer (conjugated molecule) are important.     

Scanning tunneling microscopy studies of monolayer templates: alkylthioethers and alkylethers

Scanning tunneling microscopy has been used to determine the molecular ordering in stable, ordered monolayers formed from long-chain normal and substituted alkanes in solution on highly oriented pyrolytic graphite surfaces. Monolayers were initially formed using an overlying solution of either a symmetrical dialkylthioether or a symmetrical dialkylether. Initially pure thioether solutions were then changed to nearly pure solutions of the identical chain-length ether, and vice versa. The direct application of a pure solution of long-chain symmetrical ethers onto graphite produced a lamellate monolayer within which the individual molecular axes were oriented at an angle of approximately 65 degrees to the lamellar axes. In contrast, a pure solution of long-chain symmetrical thioethers on graphite produced a monolayer within which the molecular axes were oriented perpendicular to the lamellar axes. When ethers were gradually added to solutions overlying pure thioether monolayers, the ethers substituted into the existing monolayer structure. Thus, the ether molecules could be forced to orient in the perpendicular thioether-like manner through the use of a thioether template monolayer. Continued addition of ethers to the solution ultimately produced a nearly pure ether monolayer that retained the orientation of the thioether monolayer template. However, a monolayer of thioether molecules formed by gradual substitution into an ether monolayer did not retain the 65 degrees orientation typical of dialkylethers, but exhibited the 90 degrees orientation typical of dialkylthioether monolayers. The thioethers and ethers were easily distinguished in images of mixed monolayers, allowing both an analysis of the distribution of the molecules within the mixed monolayers and a comparison of the monolayer compositions with those of the overlying solutions. Substitution of molecules into the template monolayer did not proceed randomly; instead, a molecule within a monolayer was more likely to be replaced by a molecule in the overlying solution if it was located next to a molecule that had already been replaced.     

Influence of the environment on photoinduced electron transfer: comparison between organized monolayers at the air-water interface and monolayer assemblies on glass

Photoinduced electron transfer (PET) has been investigated in organized monolayers at the air-water interface and in monolayer assemblies on glass in an effort to evaluate the influence of solvent reorganization and molecular dynamics on PET. The donor monolayer contained an amphiphilic thiacyanine dye, and the electron acceptors were methyl viologen and dioctadecyl viologen, respectively. The distance dependence is described here by a hard disk model, where an acceptor molecule within a disk with a radius rDA around the excited donor molecule quenches the donor fluorescence due to electron transfer. Acceptor molecules outside the disk are considered ineffective. The critical radius rDA is larger in monolayer assemblies on glass (rDA = 1.97 nm) than at the air-water interface (rDA = 1.15 nm) as evaluated from steady-state fluorescence quenching. This large difference indicates that the time between thermal collisions generating and destroying the energetic match required for electron tunneling from the excited donor molecule to the acceptor is quite different in the two systems that are compared.     

Mitochondrial creatine kinase adsorption to biomimetic membranes: a Langmuir monolayer study

Interaction of mitochondrial creatine kinase (mtCK) with either synthetic or natural zwitterionic or acidic phospholipids was monitored by surface pressure measurements. Injection of mtCK beneath a monolayer at very low surface pressure results in a large increase in the apparent area per lipid molecule reflecting the intrinsic surface activity of the protein. This effect is particularly pronounced with anionic phospholipid-containing films. Upon compression to high lateral pressure, the protein is squeezed out of the lipid monolayer. On the contrary, mtCK injected beneath a monolayer compressed at 30 mN/m, does not insert into the monolayer but is concentrated below the surface by anionic phospholipids as evidenced by the immediate and strong increase in the apparent molecular area occurring upon decompression. Below 8 mN/m the protein adsorbs to the interface and remains intercalated until the lateral pressure increases again. The critical pressure of insertion is higher for anionic lipid-containing monolayers than for films containing only zwitterionic phospholipids. In the former case it is markedly diminished by NaCl. The adsorption of mtCK depends on the percentage of negative charges carried by the monolayer and is reduced by increasing NaCl concentrations. However, the residual interaction existing in the absence of a global negative charge on the membrane may indicate that this interaction also involves a hydrophobic component.     

The model of the action mechanism of SP-C in the lung surfactant monolayers

The action mechanism of surfactant protein C (SP-C) in the lung surfactant monolayers is studied. On the basis of the SP-C molecular structure, a detailed interaction model is developed to describe the interaction of phospholipids/SP-C in the lung surfactant monolayers. It is supposed that: (1) in an alveolus monolayer, SP-C molecules are surrounded by phosphatidylglycerol (PG). When the monolayer is compressed, SP-C molecules can promote PG molecules to be squeezed out; (2) during compressing of the monolayer, unsaturated-PG molecules form a collapse pit firstly when liquid-expanded state (LE) components achieve the collapse pressure. Then, SP-C's alpha-helix is attracted by the collapse pit and both alpha-helix and PG molecules are squeezed out speedily. Finally, the squeezed-out matters can form a lipid-protein aggregation in the subphase. The lipid-protein aggregation, in the centre of which, there is the hydrophobic alpha-helix section surrounded by PG molecules; (3) during the monolayer expanding, because of the increasing of the monolayer's surface tension, the structure of the lipid-protein aggregation is disturbed and reinserts into the surface of the monolayer rapidly. On the basis of analyzing the energies change of the squeeze-out process, a mathematical model is obtained to calculate the squeezed-out number of DPPG molecules when a SP-C molecule squeezes out in a monolayer. According to the model, it is concluded that SP-C has the capability to promote the squeeze-out and the reinsertion of most of PG component in an alveolus monolayer, the prediction data agree well with the experimental data.     

Hydrogen peroxide reduction on amalgamated platinum electrodes covered with a monolayer of stearic acid

The reduction of hydrogen peroxide and, for comparison, oxygen on an amalgamated platinum electrode covered with a monolayer of stearic acid is studied by methods of polarization curves and impedance spectroscopy. In contrast with the oxygen reduction, the reduction of dissolved hydrogen peroxide occurs predominantly on the monolayer surface, rather than inside it. This is explained by the difficulty of penetration of the polar molecule of hydrogen peroxide into hydrocarbon environment.     

New method to measure packing densities of self-assembled thiolipid monolayers

For a monolayer of 2,3-di-phytanyl-sn-glycerol-1-tetraethylene glycol-D,L-a-lipoic acid ester lipid (DPTL) self-assembled (SAM) at a gold electrode surface we propose a new method to determine the charge number per adsorbed molecule and the packing density (area per molecule) in the monolayer. The method relies on chronocoulometry to measure the charge density at the SAM covered gold electrode surface. Two series of measurements have to be performed. In the first series, charge densities are measured for a monolayer transferred from the air-solution to the metal-solution interface using the Langmuir-Blodgett (LB) technique. This series of measurements allows one to determine charge numbers per adsorbed DPTL molecule. The second series is performed using a gold electrode covered with a self-assembled monolayer. The charge densities obtained in this series are then used to calculate the packing density with the help of charge numbers per adsorbed DPTL determined in the first series. The area per adsorbed molecule determined by the new method was compared to the area per molecule determined by the popular reductive desorption method. The molecular area determined with the new method is about 20% larger than the area calculated from the van der Waals model, which is a physically reasonable result. In contrast, the popular reductive desorption method gives an area per molecule 20% lower than the minimum estimated based on a van der Waals model. This is a physically unreasonable result. It is also shown that the charge numbers per adsorbed molecule depend on the electrode potential and may assume values smaller than the number of electrons participating in the reductive desorption step. An explanation of the origin of the "partial charge numbers" is provided. We recommend the new method be used in future studies of thiol adsorption at metal surfaces.     

Molecular printboards: monolayers of beta-cyclodextrins on silicon oxide surfaces

Monolayers of beta-cyclodextrin host molecules have been prepared on SiO2 surfaces. An ordered and stable cyano-terminated monolayer was modified in three consecutive surface reactions. First, the cyanide groups were reduced to their corresponding free amines using Red Al as a reducing agent. Second, 1,4-phenylene diisothiocyanate was used to react with the amine monolayer where it acts as a linking molecule, exposing isothiocyanates that can be derivatized further. Finally, per-6-amino beta-cyclodextrin was reacted with these isothiocyanate functions to yield a monolayer exposing beta-cyclodextrin. All monolayers were characterized by contact angle measurements, ellipsometric thickness measurements, Brewster angle Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry, which indicate the formation of a densely packed cyclodextrin surface. It was demonstrated that the beta-cyclodextrin monolayer could bind suitable guest molecules in a reversible manner. A fluorescent molecule (1), equipped with two adamantyl groups for complexation, was adsorbed onto the host monolayer from solution to form a monolayer of guest molecules. Subsequently, the guest molecules were desorbed from the surface by competition with increasing beta-cyclodextrin concentration in solution. The data were fitted using a model. An intrinsic binding constant of 3.3 +/- 1 x 10(5) M(-1) was obtained, which corresponds well to previously obtained results with a divalent guest molecule on beta-cyclodextrin monolayers on gold. In addition, the number of guest molecules bound to the host surface was determined, and a surface coverage of ca. 30% was found.     

Phase behavior and viscoelastic properties of trisilanolcyclohexyl-POSS at the air/water interface

A trisilanol polyhedral oligomeric silsesquioxane (POSS), trisilanolcyclohexyl-POSS (TCyP), has recently been reported to undergo a series of phase transitions from traditional Langmuir monolayers to unique rodlike hydrophobic aggregates in multilayer films that are different from "collapsed" morphologies seen in other systems at the air/water interface. This paper focuses on the phase transitions and morphology of films varying in average thickness from monolayers to trilayers and the corresponding viscoelastic properties of trisilanolcyclohexyl-POSS molecules at the air/water interface by means of surface pressure-area per molecule (Pi-A) isotherms, Brewster angle microscopy (BAM), and interfacial stress rheometry (ISR) measurements. The morphology studies by BAM reveal that the TCyP monolayer can collapse into different 3D structures by homogeneous or heterogeneous nucleation mechanisms. For homogeneous nucleation, analysis by Vollhardt et al.'s nucleation and growth model reveals that TCyP collapse is consistent with instantaneous nucleation with hemispherical edge growth at Pi = 3.7 mN.m(-1). Both surface storage (Gs') and loss (Gs") moduli obtained by ISR reveal three different non-Newtonian flow regimes that correlate with phase transitions in the Pi-A isotherms: (A) A viscous liquidlike "monolayer"; (B) a "biphasic regime"between a liquidlike viscous monolayer and a more rigid trilayer; and (C) an elastic solidlike "trilayer". These observations provide interesting insights into collapse mechanisms and structures in Langmuir films.     

Observation of zinc phthalocyanine aggregates on a water surface using grazing incidence X-ray scattering

Reported here are the structural properties of a zinc 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine Langmuir monolayer on a water surface under progressive lateral compression investigated by grazing incidence X-ray scattering. Grazing incidence diffuse X-ray scattering out of the specular plane (GIXOS) is exploited to determine specular reflectivity-like information where the phase change of flat-lying molecules on the surface to edge-standing molecules perpendicular to the surface is directly observed. Furthermore, grazing incident X-ray diffraction (GIXD) is used to investigate the in-plane ordering of the system where it has been found that in the high-density state (approximately 0.35 nm2 per molecule) the system can be considered to be a monolayer consisting of arrays of side-by-side lying cofacially aggregated cylindrical rodlike entities.     

Single molecular detection of a perylene dye dispersed in a Langmuir-Blodgett fatty acid monolayer using surface-enhanced resonance Raman scattering

The Langmuir-Blodgett (LB) monolayer technique was used to fabricate single molecule LB monolayer containing bis(phenethylimido)perylene (PhPTCD), a red dye dispersed in arachidic acid (AA) with an average doping of 1 molecule per microm2. The monolayer was transferred onto Ag island films to obtain spatially resolved surface-enhanced resonance Raman scattering (SERRS) spectra. The mixed LB monolayers were fabricated with a concentration, on average, of 1, 6, 19 and 118 PhPTCD molecules per microm2 in AA. The AA provides a two-dimensional host matrix whose background signal does not interfere with the detection of the probe molecule's SERRS signal. The properties of the single molecule detection were investigated using micro-Raman with a 514.5-nm laser line. The Ag island surfaces coated with the LB monolayer were mapped with spatial steps of 3 microm and global chemical imaging of the most intense SERRS band in the spectrum was also recorded. The SERRS and surface-enhanced fluorescence (SEF) of the neat and single molecule LB monolayer were recorded in a temperature range from liquid nitrogen to + 200 degrees C. Neat PhPTCD LB monolayer spectra served as reference for the identification of characteristic signatures of the single molecule behavior. The spatial resolution of Raman-microscopy experiments, the multiplicative effect of resonance Raman and SERRS, and the high sensitivity of the new dispersive Raman instruments, allow SERRS to be part of the family of single molecular spectroscopies.     

二维蛋白质分子印迹聚合物

本文对二维蛋白质分子印迹进行了综述：介绍了二维蛋白分子印迹的基本概念;阐述了常见二维蛋白质分子印迹方法的基本原理,包括表位印迹法、溶胶-凝胶法、射频光电等离子沉积法和Langmuir单层法等;根据二维蛋白分子印迹材料的不同形式,详细叙述了二维蛋白质分子印迹薄膜、核-壳微球、纳米线、Langmuir脂质体单层的制备过程、结合能力、选择识别性能;分析了目前二维蛋白质分子印迹技术存在的一些不足和进一步研究的方向。     

Studies of adsorption of 2,2′-bipyridyl on the surface of highly regulated silica matrix of the MCM-41 type by means of <Superscript>15</Superscript>N NMR spectroscopy

The study of 2,2′-bipyridyl adsorption on the surface of highly regular MCM-41 silica at 300 and 130 K was carried out by the ¹⁵N NMR spectroscopy. It was shown that at 300 K the adsorbed molecules were involved in the processes of isotropic reorientation accompanied by the formation and rupture of hydrogen bonds with the surface-located hydroxy groups. Each molecule of 2,2′-bipyridyl forms no more than one hydrogen bond at a time, and their surface density is about one molecule per 1 nm² of the surface. At 130 K 2,2′-bipyridyl forms a monolayer on the surface of silica including about 1.6 molecule per 1 nm². In this monolayer each molecule forms a hydrogen bond with one hydroxy group and prevents the interaction of the other bipyridyl molecules with one more hydroxy group.     

The Electron Spin as a Chiral Reagent

We show that enantioselective reactions can be induced by the electron spin itself and that it is possible to replace a conventional enantiopure chemical reagent by spin‐polarized electrons that provide the chiral bias for enantioselective reactions. Three examples of enantioselective chemistry resulting from electron‐spin polarization are presented. One demonstrates the enantioselective association of a chiral molecule with an achiral self‐assembled monolayer film that is spin‐polarized, while the other two show that the chiral bias provided by the electron helicity can drive both reduction and oxidation in enantiospecific electrochemical reactions. In each case, the enantioselectivity does not result from enantiospecific interactions of the molecule with the ferromagnetic electrode but from the polarized spin that crosses the interface between the substrate and the molecule. Furthermore, the direction of the electron‐spin polarization defines the handedness of the enantioselectivity. This work demonstrates a new mechanism for realizing enantioselective chemistry.