Molecular-level measurements

Since around the mid-1990s, there has been a proliferation of hydrate time-dependent studies. These include macroscopic, mesoscopic, and molecular-level measurements and modeling efforts. A proliferation of kinetic measurements marks the maturing of hydrates as a field of research. Typically, research efforts begin with the consideration of time-independent thermodynamic equilibrium properties due to relative ease of measurement. As an area matures and phase equilibrium thermodynamics becomes better defined, research generally turns to time-dependent measurements such as kinetics and transport properties. 

Li, L.J., neischmann, M. and Peter, L.M. (1989) Molecular level measurements of the kinetics of nucleation of a-lead dioxide on carbon microelectrodes. Electrochimica Acta, 34, 475. 

The development of scanning probe microscopies and x-ray reflectivity (see Chapter VIII) has allowed molecular-level characterization of the structure of the electrode surface after electrochemical reactions [145]. In particular, the important role of adsorbates in determining the state of an electrode surface is illustrated by scanning tunneling microscopic (STM) images of gold (III) surfaces in the presence and absence of chloride ions [153]. Electrodeposition of one metal on another can also be measured via x-ray diffraction [154]. 

The interface between a solid and its vapor (or an inert gas) is discussed in this chapter from an essentially phenomenological point of view. We are interested in surface energies and free energies and in how they may be measured or estimated theoretically. The study of solid surfaces at the molecular level, through the methods of spectroscopy and diffraction, is taken up in Chapter VIII. 

Interactions between macromolecules (protems, lipids, DNA,.. . ) or biological structures (e.g. membranes) are considerably more complex than the interactions described m the two preceding paragraphs. The sum of all biological mteractions at the molecular level is the basis of the complex mechanisms of life. In addition to computer simulations, direct force measurements [98], especially the surface forces apparatus, represent an invaluable tool to help understand the molecular interactions in biological systems. 

Molecular dynamics (MD) metliods can be used to simulate tribological phenomena at a molecular level. These have been used primarily to simulate behaviour observed in AFM and SFA measurements. Such simulations are limited to short-timescale events, but provide a weaitli of infonnation and insight into tribological phenomena at a level of detail tliat cannot be realized by any experimental metliod. One of tire most interesting contributions of molecular dynamics... 

Because of their hydrophobic nature, siUcones entering the aquatic environment should be significantly absorbed by sediment or migrate to the air—water interface. SiUcones have been measured in the aqueous surface microlayer at two estuarian locations and found to be comparable to levels measured in bulk (505). Volatile surface siloxanes become airborne by evaporation, and higher molecular weight species are dispersed as aerosols. 

At the molecular level, microcystins are potent inhibitors of protein phosphatases 1 and 2A. The activity of protein phosphatases can be determined by measuring... 

The SFA, originally developed by Tabor and Winterton [56], and later modified by Israelachvili and coworkers [57,58], is ideally suited for measuring molecular level adhesion and deformations. The SFA, shown schematically in Fig. 8i,ii, has been used extensively to measure forces between a variety of surfaces. The SFA combines a Hookian mechanism for measuring force with an interferometer to measure the distance between surfaces. The experimental surfaces are in the form of thin transparent films, and are mounted on cylindrical glass lenses in the SFA using an appropriate adhesive. SFA has been traditionally employed to measure forces between modified mica surfaces. (For a summary of these measurements, see refs. [59,60].) In recent years, several researchers have developed techniques to measure forces between glassy and semicrystalline polymer films, [61-63] silica [64], and silver surfaees [65,66]. The details on the SFA experimental procedure, and the summary of the SFA measurements may be obtained elsewhere (see refs. [57,58], for example.). 

Israelachvili and coworkers [64,69], Tirrell and coworkers [61-63,70], and other researchers employed the SFA to measure molecular level adhesion and deformation of self-assembled monolayers and polymers. The pull-off force (FJ, and the contact radius (a versus P) are measured. The contact radius, the local radius of curvature, and the distance between the surfaces are measured using the optical interferometer in the SFA. The primary advantage of using the SFA is its ability to study the interfacial adhesion between thin films of relatively high... 

As reviewed so far, the contact-mechanics-based techniques (JKR and SFA methods) have been effective in the understanding molecular level mechanisms related to the adhesion of elastomers and in measuring the surface and interfacial energies of polymers and self-assembled monolayers. The current work in this area is aimed at understanding contact induced interfacial rearrangements and the role of specific interactions. The recent progress of these studies is discussed in this section. 

The study of acid-base interaction is an important branch of interfacial science. These interactions are widely exploited in several practical applications such as adhesion and adsorption processes. Most of the current studies in this area are based on calorimetric studies or wetting measurements or peel test measurements. While these studies have been instrumental in the understanding of these interfacial interactions, to a certain extent the interpretation of the results of these studies has been largely empirical. The recent advances in the theory and experiments of contact mechanics could be potentially employed to better understand and measure the molecular level acid-base interactions. One of the following two experimental procedures could be utilized (1) Polymers with different levels of acidic and basic chemical constitution can be coated on to elastomeric caps, as described in Section 4.2.1, and the adhesion between these layers can be measured using the JKR technique and Eqs. 11 or 30 as appropriate. For example, poly(p-amino styrene) and poly(p-hydroxy carbonyl styrene) can be coated on to PDMS-ox, and be used as acidic and basic surfaces, respectively, to study the acid-base interactions. (2) Another approach is to graft acidic or basic macromers onto a weakly crosslinked polyisoprene or polybutadiene elastomeric networks, and use these elastomeric networks in the JKR studies as described in Section 4.2.1. 

The constancy of properties at equilibrium refers to macroscopic measurements. Now we will consider what the equilibrium is like on the molecular level, as chemists picture it. 

In Chapter 1 we saw that the Boltzmann equation S = k log W gives the same qualitative relationship between entropy and disorder and suggested that a fundamental property of entropy is a measure of the disorder in a system. In Chapter 10 we will explore this relationship in more detail on the molecular level, and use the Boltzmann expression to develop quantitative relationships between entropy and disorder. 

Although significant insight into the process of bond rupture has been gathered from the studies on the scission kinetics, it remains desirable at this stage to carry out further experimentation at a molecular level to get information on the chain conformation at the moment of fracture. As a first step in this direction, birefringence measurements have been attempted recently in the single jet cell... 

There are still other surface analysis techniques including ellipsometry, surface enhanced Raman scattering, light scattering, nano-hardness measurements etc. which are used for specific investigations. It is, however, already evident from this discussion that many new and powerful techniques now are available which offer the capability of investigating various aspects of polymer surfaces on a molecular level. Some of those techniques are surface specific while others can be used for the analysis of buried interfaces, too. 

Such approximation is valid when the thickness of the polymeric layer is small compared to die thickness of die crystal, and the measured frequency change is small with respect to the resonant frequency of the unloaded crystal. Mass changes up to 0.05% of die crystal mass commonly meet this approximation. In die absence of molecular specificity, EQCM cannot be used for molecular-level characterization of surfaces. Electrochemical quartz crystal microbalance devices also hold promise for the task of affinity-based chemical sensing, as they allow simultaneous measurements of both tile mass and die current. The principles and capabilities of EQCM have been reviewed (67,68). The combination of EQCM widi scanning electrochemical microscopy has also been reported recently for studying die dissolution and etching of various thin films (69). The recent development of a multichannel quartz crystal microbalance (70), based on arrays of resonators, should further enhance die scope and power of EQCM. 

Metcalfe The group of Professor Metcalfe has combined kinetic and work function measurements to investigate the electrochemical promotion of CO oxidation on Pt/YSZ and, more recently, had made important modeling advances for the fundamental description of electrochemical promotion at the molecular level. 

In 1877, the Austrian physicist Ludwig Boltzmann proposed a molecular definition of entropy that enables us to calculate the absolute entropy at any temperature (Fig. 7.6). His formula provided a way of calculating the entropy when measurements could not be made and deepened our insight into the meaning of entropy at the molecular level. The Boltzmann formula for the entropy is... 

Much of the pioneering work which led to the discovery of efficient catalysts for modern Industrial catalytic processes was performed at a time when advanced analytical Instrumentation was not available. Insights Into catalytic phenomena were achieved through gas adsorption, molecular reaction probes, and macroscopic kinetic measurements. Although Sabatier postulated the existence of unstable reaction Intermediates at the turn of this century. It was not until the 1950 s that such species were actually observed on solid surfaces by Elschens and co-workers (2.) using Infrared spectroscopy. Today, scientists have the luxury of using a multitude of sophisticated surface analytical techniques to study catalytic phenomena on a molecular level. Nevertheless, kinetic measurements using chemically specific probe molecules are still the... 

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