Dynamic properties of molecularly thin liquid films

An experimental technique is described for simultaneously measuring the static and dynamic interactions of very thin liquid films between two surfaces as they are moved normally or laterally relative to each other. Film thickness can be measured and controlled to 1 angstrom. Initial results are presented of the transition in the physical properties of liquid films only one molecular layer thick to thicker films whose properties are practically indistinguishable from the bulk. In particular, the results show that two molecularly smooth surfaces, when close together in simple liquids, slide (shear) past each other while separated by a discrete number of molecular layers, and that the frictional force is "quantized" with the number of layers.     

Molecular mechanisms and forces involved in the adhesion and fusion of amphiphilic bilayers

The surface forces apparatus technique was used for measuring the adhesion, deformation, and fusion of bilayers supported on mica surfaces in aqueous solutions. The most important force leading to the direct fusion of bilayers is the hydrophobic interaction, although the occurrence of fusion is not simply related to the force law between bilayers. Bilayers do not need to "overcome" some repulsive force barrier, such as hydration, before they can fuse. Instead, once bilayer surfaces come within about 1 nanometer of each other, local deformations and molecular rearrangements allow them to "bypass" these forces.     

Forces between surfaces in liquids

Recent developments in the direct measurements of forces between surfaces in liquids at the ?ngstrom resolution level are reviewed. The results reveal a rich variety of interactions and interaction potentials that depend on the nature of the surfaces and intervening liquids. These results also shed new insights into liquid structure adjacent to surfaces and the interactions occurrig in complex systems, with implications in many different areas of chemical physics, biology, and technology. The origin of some important fundamental interactions, such as repulsive "hydration" forces and attractive "hydrophobic" forces, are still not understood and offer a challenge for experimental and theoretical work in this area.     

Supramolecular Materials: Self-Organized Nanostructures

Miniaturized triblock copolymers have been found to self-assemble into nanostructures that are highly regular in size and shape. Mushroom-shaped supramolecular structures of about 200 kilodaltons form by crystallization of the chemically identical blocks and self-organize into films containing 100 or more layers stacked in a polar arrangement. The polar supramolecular material exhibits spontaneous second-harmonic generation from infrared to green photons and has an adhesive tape-like character with nonadhesive-hydrophobic and hydrophilic-sticky opposite surfaces. The films also have reasonable shear strength and adhere tenaciously to glass surfaces on one side only. The regular and finite size of the supramolecular units is believed to be mediated by repulsive forces among some of the segments in the triblock molecules. A large diversity of multifunctional materials could be formed from regular supramolecular units weighing hundreds of kilodaltons.     

Cavitation and the interaction between macroscopic hydrophobic surfaces

The interaction in water of neutral hydrocarbon and fluorocarbon surfaces, prepared by Langmuir-Blodgett deposition of surfactant monolayers, has been investigated. The attraction between these hydrophobic surfaces can be measured at separations of 70 to 90 nanometers and thus is of considerably greater range than previously found. Spontaneous cavitation occurred as soon as the fluorocarbon surfaces were brought into contact but occurred between the hydrocarbon surfaces only after separation from contact. The very long range forces measured are a consequence of the metastability of water films between macroscopic hydrophobic surfaces. Thus the hydrophobic interaction between macroscopic surfaces may not be related to water structure in the same way that the hydrophobic effect between nonpolar molecules is related to water structure.     

Spontaneous vesicles formed from hydroxide surfactants: evidence from electron microscopy

Dialkyldimethylammonium hydroxide surfactants are highly soluble in water and form spontaneous stable vesicles. These vesicles can be grown to size with added acid, and appear to provide an ideal membrane mimetic system for the study of fusion and ion transport. These phenomena are a consequence of strong hydration forces that are not necessarily limited to the hydroxide ions. The forces can be used to design a variety of model systems whose behavior differs from that of systems in which double-chained surfactants form insoluble liquid crystalline phases in water and unstable vesicle suspensions on prolonged sonication.     

户外用压缩防腐木——ACQ——D木材的处理技术初探

为研究压缩处理在木材防腐方面的应用,该研究测定了经过不同水浴和喷水预处理后的径向压缩木材在胺溶铜季铵盐--D型防腐剂中浸泡后的吸液量和变形回复率,并测定了由此制备得到的压缩防腐木的表面硬度、厚度方向上的密度分布和CuO保持量分布情况。结果表明:①变形回复率和吸液量之间有很好的对应关系,一般变形回复率越大,吸液量也越大;②经过预处理的压缩试材和素材相比,吸液量可以提高1.5倍左右,表面硬度可提高3～4倍;未经预处理的压缩试材和素材相比,吸液量可以提高2倍以上,但是表面硬度的提高不大;③ 经过预处理的压缩防腐木,其厚度方向上的密度分布比较均匀,另外CuO的保持量比未经预处理的压缩防腐木高,并且呈现表层高、逐步向内层递减的趋势。由此看出,由该研究方法制备的压缩防腐木可同时实现表面密实化和提高防腐性能的目的,尤其适用于户外设施中。      

预热温度对层状压缩木材力学性能的影响

不同预热温度下形成的层状压缩木材,因压缩层位置差异形成的不同结构及预热温度本身的变化均会引起力学性能变化。以毛白杨Populus tomentosa弦向板为材料,采用水热控制方法,通过改变预热温度获得了压缩层位于表层至中心层的不同结构的层状压缩木材。对其表面硬度、木材硬度、抗弯弹性模量与抗弯强度进行对比研究。结果表明:①随着预热温度的升高,木材表面硬度显著升高（P < 0.01）,较对照的增加率为3.9%~57.2%,而木材硬度则极显著降低（P < 0.001）,较对照的增加率为8.6%~38.5%。这个结果与压缩层随着预热温度升高,逐渐由表层向中心层移动形成的表层下0.32和2.82 mm厚度范围内木材的平均密度变化以及高温的作用密切相关。②随着预热温度的升高,弦向弯曲弹性模量逐渐增大,径向弯曲弹性模量逐渐减小;抗弯强度先增大,150℃后逐渐减小;但抗弯性能无显著差异（P>0.05）。不同预热温度下形成的层状压缩木材的力学性主要受其结构的影响,其次是温度的影响。控制压缩层的位置出现于木材表层,同时提高压缩层的密度,可获得力学性能更好的层状压缩木材。     

Molecular interactions and hydrogen bond tunneling dynamics: some new perspectives

The recent development of tunable far-infrared lasers and other high-resolution spectroscopic probes of weakly bound clusters is having a significant impact on our understanding of intermolecular forces and on the complex quantum tunneling dynamics that occur in hydrogen-bonded systems. Far-infrared studies of a variety of interactions are discussed, including several prototypical water-hydrophobe complexes, the water trimer, and the ammonia dimer. Particular attention is paid to the inversion of spectroscopic data to yield detailed intermolecular potential energy surfaces. Investigations of nonpairwise additivity are also described.     

Adhesion and friction mechanisms of polymer-on-polymer surfaces

The adhesion and friction of smooth polymer surfaces were studied below the glass transition temperature by use of a surface forces apparatus. The friction force of a crosslinked polymer was orders of magnitude less than that of an uncrosslinked polymer. In contrast, after chain scission of the outermost layers, the adhesion hysteresis and friction forces increase substantially. These results show that polymer-polymer adhesion hysteresis and friction depend on the dynamic rearrangement of the outermost polymer segments at shearing interfaces, and that both increase as a transition is made from crosslinked surfaces to surfaces with long chains to surfaces with quasi-free ends. The results suggest new ways for manipulating the adhesion and friction of polymer surfaces by adjusting the state of the surface chains.     

The force needed to move an atom on a surface

Manipulation of individual atoms and molecules by scanning probe microscopy offers the ability of controlled assembly at the single-atom scale. However, the driving forces behind atomic manipulation have not yet been measured. We used an atomic force microscope to measure the vertical and lateral forces exerted on individual adsorbed atoms or molecules by the probe tip. We found that the force that it takes to move an atom depends strongly on the adsorbate and the surface. Our results indicate that for moving metal atoms on metal surfaces, the lateral force component plays the dominant role. Furthermore, measuring spatial maps of the forces during manipulation yielded the full potential energy landscape of the tip-sample interaction.     

Protein hydration in aqueous solution

High-resolution proton nuclear magnetic resonance studies of protein hydration in aqueous solution show that there are two qualitatively different types of hydration sites. A well-defined, small number of water molecules in the interior of the protein are in identical locations in the crystal structure and in solution, and their residence times are in the range from about 10(-2) to 10(-8) second. Hydration of the protein surface in solution is by water molecules with residence times in the subnanosecond range, even when they are located in hydration sites that contain well-ordered water in the x-ray structures of protein single crystals.     

Isolating the spectroscopic signature of a hydration shell with the use of clusters: superoxide tetrahydrate

Cluster spectroscopy, aided by ab initio theory, was used to determine the detailed structure of a complete hydration shell around an anion. Infrared spectra of size-selected O(2)-. (H(2)O)(n) (n = 1 to 4) cluster ions were obtained by photoevaporation of an argon nanomatrix. Four water molecules are required to complete the coordination shell. The simple spectrum of the tetrahydrate reveals a structure in which each water molecule is engaged in a single hydrogen bond to one of the four lobes of the pi* orbital of the superoxide, whereas the water molecules bind together in pairs. This illustrates how water networks deform upon accommodating a solute ion to create a distinct supramolecular species.     

Atomic arrangements at metal surfaces

The termination of a solid induces changes in the locations of the outermost atoms of the solid. The changes can be minor or as dramatic as the rearrangement of the atoms into a different crystallographic group. Surface crystallography studies have determined that all surfaces are altered by forces induced at the solid-vacuum interface. At the least, the outermost atomic layers are displaced away from positions that they would have had in the bulk environment. Results from experimental and theoretical investigations for the Al(110) surface are discussed to illustrate present understanding of the surface atomic displacements. Some effects that the truncation- induced forces have on the surfaces of binary metal alloys are also discussed.     

Helix geometry, hydration, and G.A mismatch in a B-DNA decamer

The DNA double helix is not a regular, featureless barberpole molecule. Different base sequences have their own special signature, in the way that they influence groove width, helical twist, bending, and mechanical rigidity or resistance to bending. These special features probably help other molecules such as repressors to read and recognize one base sequence in preference to another. Single crystal x-ray structure analysis is beginning to show us the various structures possible in the B-DNA family. The DNA decamer C-C-A-A-G-A-T-T-G-G appears to be a better model for mixed-sequence B-DNA than was the earlier C-G-C-G-A-A-T-T-C-G-C-G, which is more akin to regions of poly(dA).poly(dT). The G.A mismatch base pairs at the center of the decamer are in the anti-anti conformation about their bonds from base to sugar, in agreement with nuclear magnetic resonance evidence on this and other sequences, and in contrast to the anti-syn geometry reported for G.A pairs in C-G-C-G-A-A-T-T-A-G-C-G. The ordered spine of hydration seen earlier in the narrow-grooved dodecamer has its counterpart, in this wide-grooved decamer, in two strings of water molecules lining the walls of the minor groove, bridging from purine N3 or pyrimidine O2, to the following sugar O4'. The same strings of hydration are present in the phosphorothioate analog of G-C-G-C-G-C. Unlike the spine, which is broken up by the intrusion of amine groups at guanines, these water strings are found in general, mixed-sequence DNA because they can pass by unimpeded to either side of a guanine N2 amine. The spine and strings are perceived as two extremes of a general pattern of hydration of the minor groove, which probably is the dominant factor in making B-DNA the preferred form at high hydration.     

Direct determination of ionic solvation from neutron diffraction

Much information on ionic solvation in electrolyte solutions has been inferred from macroscopic thermodynamic and transport properties and from spectroscopy. These ion-water interactions can now be probed directly and unambiguously by neutron diffraction. Such measurements have been done with neodymium trichloride solutions in heavy water that are identical in every respect except the isotopic state of the neodymium ions; these experiments yield in a straightforward manner the distribution of oxygen and deuterium atoms from the water molecules in the first hydration sphere of the neodymium ion. Each ion is surrounded by 8.6 oxygen atoms at a distance of 2.48 angstroms and 16.7 deuterium atoms at 3.13 angstroms indicating a well-defined first hydration sphere of water molecules, the deuterium atoms pointing away from the cation.     

Detection of molecular alignment in confined films

Optical second harmonic generation was used to study the in-plane alignment of self-assembled silane monolayers attached to a glass surface under mechanical loading. The measurements allow correlation of the macroscopic forces acting on the monolayer with the average orientation and the azimuthal molecular alignment of the terminal molecular entity. Compression and shear forces lead to an alignment of the initially randomly oriented molecules on a macroscopic length scale. The change in azimuthal alignment of molecules under mechanical stress was found to be irreversible on the time scale of 12 hours, whereas changes of the molecular tilt angle were reversible.     

Attractive forces between uncharged hydrophobic surfaces: direct measurements in aqueous solution

Long, double-chained alkylammonium acetate surfactants are soluble in water and, under suitable conditions, adsorb onto sheets of muscovite mica, forming an electrically neutral, hydrophobic surface. Attractive forces measured between such surfaces are 10 to 100 times stronger than expected from van der Waals theory over distances D up to about 10 nanometers. The forces decay exponentially [with a force proportional to exp(-D/1.4)] instead of following the power-law behavior of continuum theory. The results of these and earlier experiments indicate that the strength of these attractive forces depends critically on the degree of hydrophobicity of the surface and is due to the long-range influence of the surface on the structure of water. In addition, for very hydrophobic surfaces, the cavitation effects on pulling the surfaces apart are described.     

Membrane permeability: monolayer relationships

A model of permeation of living membranes is proposed in which penetration by polar molecules takes place through islands composed of limited numbers of lipoidal molecules in a state comparable to that of certain compressed monolayers. These islands are visualized as scattered within a rigid, relatively impervious matrix. Relationships for penetration of monolayers by gases have been applied to this membrane model. Calculations on this basis demonstrate that the permeabilities relative to water are described at least as well by this model as by that assuming rigid pores of 4.25 A radius.     

Water at hydrophobic surfaces: weak hydrogen bonding and strong orientation effects

Vibrational studies that selectively probe molecular structure at CCl4/H2O and hydrocarbon/H2O interfaces show that the hydrogen bonding between adjacent water molecules at these interfaces is weak, in contrast to generally accepted models of water next to fluid hydrophobic surfaces that suggest strong hydrogen bonding. However, interactions between these water molecules and the organic phase result in substantial orientation of these weakly hydrogen-bonded water molecules in the interfacial region. The results have important implications for understanding water adjacent to hydrophobic surfaces and the penetration of water into hydrophobic phases.