Alkyl-thiol Langmuir films on the surface of liquid mercury

The coverage dependent phase behavior of monolayers of alkyl thiols (CH3(CH2)(n-1)SH, denoted as CnSH) on mercury was studied for chain lengths 9 相似文献   

Temperature dependence of the structure of Langmuir films of normal-alkanes on liquid mercury

The temperature dependent phase behavior of Langmuir films of n-alkanes [CH3(CH2)(n-2)CH3, denote Cn] on mercury was studied for chain lengths 19< or =n< or =22 and temperatures 15< or =T< or =44 degrees C, using surface tensiometry and surface x-ray diffraction methods. In contrast with Langmuir films on water, where molecules invariably orient roughly surface normal, alkanes on mercury are always oriented surface parallel and show no long-range in-plane order at any surface pressure. A gas and several condensed phases of single, double, and triple layers of lying-down molecules are found, depending on n and T. At high coverages, the alkanes studied here show transitions from a triple to a double to a single layer with increasing temperature. The transition temperature from a double to a single layer is found to be approximately 5 degrees C, lower than the bulk rotator-to-liquid melting temperature, while the transition from a triple to a double layer is about as much below the double-to-single layer transition. Both monolayer and bulk transition temperatures show a linear increase with n with identical slopes of approximately 4.5 degrees C/CH2 within the range of n values addressed here. It is suggested that the film and bulk transitions are both driven by a common cause: the proliferation of gauche defects in the chain with increasing temperature.     

Grazing Incidence X-ray diffraction on Langmuir films: toward atomic resolution

We have analyzed grazing incidence diffration (GIXD) data from condensed phases of Langmuir films of long-chain fatty acids at the air-water interface by using a new method consisting of a careful extraction of the structure factors followed by fitting of molecular parameters. We show that, contrary to the general belief, the information contained in GIXD spectra is enough to obtain near-atomic structural information. In particular, we directly determine for the first time the orientation of the chain backbone planes and of the carboxylic headgroups and we evaluate chain conformation defects. This new method allowed us to evidence a new phase of symmetry p2gm at high pressure, corresponding to a minimum in lattice energy, but never observed.     

The structure and phase diagram of Langmuir films of alcohols on mercury

The coverage-dependent phase behavior of molecular films of alcohols (CH3(CH2)n-2CH2OH, denoted as CnOH) on mercury was studied for chain lengths 8 < or = n < or = 28, using surface tensiometry and surface specific X-ray methods. Phases with surface-normal-oriented molecules are found at high coverage, showing the CS, S, and LS phases found also on water. Phases comprising surface parallel molecules, which do not exist on water, are found here at low coverage. For the lowest coverage a two-dimensional gas phase is found, followed, upon increasing the coverage, by an n-dependent sequence of condensed phases of up to four layers of surface-parallel molecules before converting to the surface-normal phases. In contrast with the surface-normal phases, all of the surface-parallel phases are found to lack long-range order in the surface-parallel direction. Adsorption energies are derived from the phase diagram for the alkyl chain and the alcohol headgroup.     

Dynamic surface tensiometry of tissues using Langmuir films

Langmuir monolayers are useful models of biomembranes as they allow simulation of biological conditions and rigorous thermodynamic analysis. This technique was used to characterize tissues at body temperature for the first time in our study. The organs studied include liver, kidney, stomach, testis, heart and brain from goat and certain human cancerous as well as their corresponding normal biopsies to reveal the potential of the tissue monolayer technique. Monolayers were formed on the surface of deionized water by spreading monolayer amounts of the tissue homogenates. The parameters calculated were minimum surface tension, relative lift off area, relative limiting area, compressibility and hysteresis area. Our results reveal that the parameters can differentiate between tissues obtained from different organs and were statistically significant using one-way ANOVA and Newman Keul's test (P<0.05). For example goat's stomach tissue had the lowest hysteresis area (DeltaG) value (27.6 microJ) whereas brain DeltaG value was nine folds higher than stomach value. Brain had the lowest minimum surface tension of 30.3+/-1.0 mN/m whereas stomach had a value of 40.5+/-0. 2 mN/m. Interestingly, the DeltaG values of human normal neck and esophageal tissues were 3.4 and 3.2 folds greater than that of their respective cancer tissues whereas the DeltaG values of vulval and breast cancer tissues were 4.6 and 4 folds greater than that of their respective normal tissues. While the gammamin values of neck cancer tissue showed 95% increase from normal tissue values, those of vulval and breast cancer tissues were 46 and 50% less compared to their respective normal tissue values. Though all the surface tensiometric parameters showed significant changes, minimum surface tension and hysteresis area were the most sensitive indicators of tissue types and diseased states. Further, the effects of therapeutics could also be monitored by this technique. This is evidenced by the post-radiotherapy tissue isotherms of neck and vulval cancers, where clinical radio-sensitivity was associated with a shift in the tensiometry towards their respective normal isotherms. The small sample amounts required, precision of the technique, very low within group variability, organ specificity and sensitivity to detect changes in diseased states make it a promising tool for prognostic evaluation of diseased states and monitoring effects of therapeutics. Further research is warranted in this promising and hitherto unexplored field of tissue tensiometry.     

X-ray scattering studies of fatty acid films on water and on Cdcl2 solutions

X-ray diffraction methods for Langmuir films on the surface of water are briefly presented, together with recent results for docosanoic acid monolayers on pure water and for eicosanoic acid monolayers on an ionic subphase.     

Structure of the surface layer of mercury and adhesion of Langmuir monolayers on it

A model crystalline approximant of the surface layer (SL) structure of liquid mercury is formed using the algorithm, previously applied to form a crystalline approximant of the SL structure of water, the experimental data on the SL structure of mercury, and the stereochemical data for Hg atoms in the α-Hg crystalline phase and bulk liquid mercury. The correspondence of the metrics of the crystalline approximant proposed for the SL structure of mercury and Langmuir monolayers composed of organic molecules with hydrocarbon tails and different hydrophilic groups on liquid mercury to the position of molecules along mercury SL is shown.     

The surface tension of liquid copper

The surface tension of liquid copper of 99.999 mass per cent purity has been measured by the sessile drop method in the temperature range 1373 to 1861 K. The least-squares equation expressing the surface tension σ as a function of temperature T is:

$\text{σ(}\text{Cu}\text{)/}\text{mN m}{}^{\mathrm{?}}\text{= (1552±35) ? (0.176±0.023)T/}\text{K}$

The linear correlation of excess surface enthalpy $\text{H}{}^{\mathrm{\sigma }}\text{A}{}^{\mathrm{\sigma }}$ and excess surface entropy $\text{S}{}^{\mathrm{\sigma }}\text{A}{}^{\mathrm{\sigma }}$ per unit area among σ(T) from the literature is also demonstrated. Estimation of $\text{S}{}^{\mathrm{\sigma }}\text{A}{}^{\mathrm{\sigma }}$ via the statistical electron-gas theory of Zadumkin and Pugachewich yields an equation for the calculation of recommended values for the surface tension of molten copper as a function of temperature:

$\text{σ(}\text{Cu}\text{)/}\text{mN m}{}^{\mathrm{?}}\text{= 1497 ? 0.174(T/}\text{K}\text{)}$

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Phage Langmuir monolayers and Langmuir–Blodgett films

Stable, insoluble Langmuir monolayer films composed of Staphylococcus aureus-specific lytic bacteriophage were formed at an air–water interface and characterized. The phage monolayer was very strong, withstanding a surface pressure of ～40 mN/m at 20 °C. The surface pressure–area (Π–A) isotherm possessed a shoulder at ～7 × 10⁴ nm²/phage particle, attributed to a change in phage orientation at the air–water interface from horizontal to vertical capsid-down/tail-up orientation as surface pressure was increased. The Π–A-dependence was accurately described using the Volmer equation of state, assuming horizontal orientation to an air–water interface at low surface pressures with an excluded area per phage particle of 4.6 × 10⁴ nm². At high pressures phage particles followed the space-filling densely packed disks model with a specific area of 8.5 × 10³ nm²/phage particle. Lytic phage monolayers were transferred onto gold-coated silica substrates from the air–water interface at a constant surface pressure of 18 mN/m by Langmuir–Blodgett method, then dried and analyzed by scanning electron microscopy (SEM) and ellipsometry. Phage specific adsorption (Γ) in Langmuir–Blodgett (LB) films measured by SEM was consistent with that calculated independently from Π–A isotherms at the transfer surface pressure of 18 mN/m (Γ = 23 phage particles/μm²). The 50 nm-thickness of phage monolayer measured by ellipsometer agreed well with the horizontal phage average size estimated by SEM. Surface properties of phage Langmuir monolayer compare well with other monolayers formed from nano- and micro-particles at the air–water interface and similar to that of classic amphiphiles 1,2-diphytanoyl-sn-glycero-3-phosphocholine (phospholipid) and stearic acid.     

Disjoining pressure and the film-height-dependent surface tension of thin liquid films: New insight from capillary wave fluctuations

In this paper we review simulation and experimental studies of thermal capillary wave fluctuations as an ideal means for probing the underlying disjoining pressure and surface tensions, and more generally, fine details of the Interfacial Hamiltonian Model. We discuss recent simulation results that reveal a film-height-dependent surface tension not accounted for in the classical Interfacial Hamiltonian Model. We show how this observation may be explained bottom-up from sound principles of statistical thermodynamics and discuss some of its implications.     

Density,viscosity, and surface tension of binary liquid systems: Ethanoic acid,propanoic acid,and butanoic acid with nitrobenzene

Density, viscosity, and surface tension of three binary liquid systems: ethanoic acid+nitrobenzene, propanoic acid+nitrobenzene, and butanoic acid+nitrobenzene have been determined at 25, 35, and 45°C, over the whole composition range. The excess molar volumes, viscosities, Gibbs energies for the activation of flow, and surface tension were evaluated and fitted to a Redlich-Kister type of equation. The Grunberg-Nissan parameter d was also calculated. Binary viscosity data were fitted to the models of McAllister, Heric, Krishnan, and Laddha, Auslander, and Teja and Rice. Surface tension data were fitted to the models of Zihao and Jufu, Rice, and Teja, and an empirical two-constant model.     

离子液体水合物反应液表面张力的研究

表面张力是衡量水合物动力学促进剂促进效果的主要参数,为了探究离子液体应用于水合物生成促进的可行性,实验合成了具有表面活性功能的离子液体[HMIPS]DBSA、[MIMPS]DBSA、[PIPS]DBSA和[PYPS]DBSA,并分别测定了在不同浓度及温度条件下的表面张力。结果表明:四种离子液体的最低表面张力相较于纯水均降低了一半以上,其中[MIMPS]DBSA的降幅最小;各离子液体的表面张力随着浓度的升高而降低并达到一定值,其中[MIMPS]DBSA的CMC浓度为700 ppm左右,其余三种离子液体的CMC浓度则均在900 ppm以上;此外,各离子液体的表面张力随着温度的升高而逐渐降低,但相较于浓度对其的影响,降幅要小得多。这说明浓度是影响水合物反应液表面张力的主要控制因素。可以发现所合成的离子液体与当前最好的促进剂SDS相比,有待于进一步优化。但离子液体的高度可设计性及生物可降解性给水合物促进剂的研发提供了广阔的发展空间,具有很好的发展前景。     

Alignment of liquid crystal and dichroic dye molecules in mixed Langmuir and Langmuir-Blodgett films

A study of dichroic dye-liquid crystal mixtures (guest-host systems) in monolayers formed at a gas-liquid interface (Langmuir films) and at a solid surface (Langmuir-Blodgett films) has been made. As a host 4- n -octyl-4′-cyanobiphenyl (8CB) or 4- n -pentyl-4″-cyano- p -terphenyl (5CT) were chosen, while three dichroic azo dyes with various molecular structures were used as guest species. The dyes were added to the liquid crystal matrices at a concentration corresponding to the whole range of molar fractions and the surface pressure-mean molecular area isotherms for Langmuir films were recorded. On the basis of the isotherms, conclusions about the molecular organization and the miscibility of the components in the ultrathin films were drawn. The Langmuir films were transferred onto the quartz plates at surface pressures below the collapse point. The polarized absorption spectra of the Langmuir-Blodgett films were recorded and information about the alignment and intermolecular interactions in the mixtures of the non-amphiphilic dichroic dyes and the liquid crystals with strongly polar terminal groups were obtained.     

Synthesis of novel amphiphilic azobenzenes and X-ray scattering studies of their Langmuir monolayers

We report a simple synthetic route to novel symmetrical alkylated and acylated amphiphilic 4,4'-diaminoazobenzene dyes, with their optical axis perpendicular to the amphiphilic direction of the molecule. Three different substitution patterns are reported, two of which are highly amphiphilic. At the air-water interface, the amphiphilic azobenzenes form noncrystalline but stable Langmuir films that display an unusual reversible monolayer collapse close to 35 mN/m. The structures and phase transitions were studied by X-ray reflectivity (XR) and grazing-incidence X-ray diffraction, both utilizing synchrotron radiation. Compression beyond the collapse point does not change the XR data, showing that the film is unchanged at the molecular level, even at areas less than half of that of the collapse. This leads to the conclusion that few macroscopic collapse sites are responsible for reversibly removing large amounts of material from the interface.     

Alignment of liquid crystal and dichroic dye molecules in mixed Langmuir and Langmuir-Blodgett films

A study of dichroic dye-liquid crystal mixtures (guest-host systems) in monolayers formed at a gas-liquid interface (Langmuir films) and at a solid surface (Langmuir-Blodgett films) has been made. As a host 4- n -octyl-4'-cyanobiphenyl (8CB) or 4- n -pentyl-4"-cyano- p -terphenyl (5CT) were chosen, while three dichroic azo dyes with various molecular structures were used as guest species. The dyes were added to the liquid crystal matrices at a concentration corresponding to the whole range of molar fractions and the surface pressure-mean molecular area isotherms for Langmuir films were recorded. On the basis of the isotherms, conclusions about the molecular organization and the miscibility of the components in the ultrathin films were drawn. The Langmuir films were transferred onto the quartz plates at surface pressures below the collapse point. The polarized absorption spectra of the Langmuir-Blodgett films were recorded and information about the alignment and intermolecular interactions in the mixtures of the non-amphiphilic dichroic dyes and the liquid crystals with strongly polar terminal groups were obtained.     

Line tension effects for liquid droplets on circular surface domains

We study the morphologies of single liquid droplets wetting a substrate in the presence of the line tension of the three-phase contact line. On a homogeneous substrate, the line tension leads to a discontinuous unbinding of the droplet if its volume is decreased below a critical value. For a droplet wetting a structured surface with a circular domain, a line tension contrast gives rise to discontinuous depinning transitions of the contact line from the domain boundary as the droplet volume is varied. We calculate the corresponding free energy bifurcation diagram analytically for axisymmetric droplet shapes. Numerical minimization of the droplet free energy shows that line tension contrasts can stabilize nonaxisymmetric droplet shapes, thus modifying the bifurcation diagram. These latter shapes should be accessible to experiments and can be used to reveal the presence of a line tension contrast.     

X-ray studies on Langmuir-Blodgett films of novel amphiphilic oligothiophenes

A new type of amphiphilic thiophene, oligo[n-alkyl-3-(3-thienyl) glutaric acid], was synthesised (with n = 8, 12 or 18). These molecules form a stable monolayer at the air/water interface. Successful Langmuir-Blodgett (LB) deposition was achieved by vertical dipping. The LB films of Y-type exhibit well-defined layered structures, as determined by X-ray diffraction measurements, with a regular molecular arrangement within the layers.     

Measurement of the surface tension of liquid marbles

The capillary rise and Wilhelmy plate methods have been used to study the "surface tension" of water marbles encapsulated with polytetrafluoroethylene (PTFE) powders of 1-, 35-, and 100-μm particle size. With the capillary rise technique, a glass capillary tube was inserted into a water marble to measure the capillary rise of the water. The Laplace pressure exerted by the water marble was directly measured by comparing the heights of the capillary rise from the marble and from a flat water surface in a beaker. An equation based on Marmur's model was proposed to calculate the water marble surface tension. This method does not require the water contact angle with the supporting solid surface to be considered; it is therefore a simple but efficient method for determining liquid marble surface tension. The Wilhelmy method was used to measure the surface tension of a flat water surface covered by PTFE powder. This method offers a new angle for investigating liquid marble shell properties. A discussion on the nature and the realistic magnitude of liquid marble surface tension is offered.