Spectroscopy total internal reflection

The thicknesses of free soap films and liquid films adsorbed on surfaces (Figs. 1.26d and 1.26e), which can be measured using optical techniques such as reflected intensity, total internal reflection spectroscopy, or ellipsometry as functions of salt concentration or vapor pressure, can provide information on the long-range repulsive forces stabilizing thick wetting films. We see an example of this in Chapter 11. 

Fluorescence and Transient Absorption Spectra of Solid Surface Development of Time-Resolved Total Internal Reflection Spectroscopy (Hiroshi Masuhara)... 

FLUORESCENCE AND TRANSIENT ABSORPTION SPECTRA OF SOLID SURFACE DEVELOPMENT OF TIME-RESOLVED TOTAL INTERNAL REFLECTION SPECTROSCOPY... 

Figure 4.3 Theory of attenuated total internal reflectance spectroscopy. (Source Author s own files)...

S. Tsukahara and H. Watarai, Transient attenuated total internal reflection spectroscopy to measure the relaxation kinetics of triplet state of tetra(N-methylpyridinium-4-yl)porphine at liquid-liquid interface, Chem. Lett., 89-90 (1999). 

Figure 7. Total internal reflection sum frequency generation (TIR-SFG) vibrational spectroscopy of high-pressure room temperature adsorption of carbon monoxide on PVP-protected Pt cube monolayers and calcined (373 K, 3h) monolayers [27], The infrared spectra demonstrate CO is adsorbed at atop sites, but is considerably red-shifted on the PVP-protected Pt cubes. After calcination, the atop frequency blueshifts to 2085 cm in good agreement with CO adsorption on Pt(l 0 0) at high coverages [28], (Reprinted from Ref [27], 2006, with permission from American Chemical Society.)...

The development of hydrodynamic techniques which allow the direct measurement of interfacial fluxes and interfacial concentrations is likely to be a key trend of future work in this area. Suitable detectors for local interfacial or near-interfacial measurements include spectroscopic probes, such as total internal reflection fluorometry [88-90], surface second-harmonic generation [91], probe beam deflection [92], and spatially resolved UV-visible absorption spectroscopy [93]. Additionally, building on the ideas in MEMED, submicrometer or nanometer scale electrodes may prove to be relatively noninvasive probes of interfacial concentrations in other hydrodynamic systems. The construction and application of electrodes of this size is now becoming more widespread and general [94-96]. 

Multiple Internal Reflection Spectroscopy (MIR) is an alternative approach in which the IR beam is passed through a thin, IR transmitting sample such that it undergoes total internal reflection alternately from the front and rear faces of the sample (Figure 3.1(b)). At each reflection, some of the IT radiation may be absorbed by species adsorbed on the solid surface. 

Recently, a formalism has been developed to determine the second and the fourth order parameters of films using polarized total internal reflection fluorescence (TIRF) [71]. Similarly to IR-ATR spectroscopy (Section 4), the experiment makes use of p- and s-polarized excitation, but the fluorescence emission (analyzed either in p- or s-direction) is detected normal to the substrate. Two approaches are developed based on the measurements of two intensity ratios. In the first one, the S angle has to be known experimentally or theoretically, and the order parameters (P2) and (P4) can be determined. In the second one, the order parameter (R ) is obtained by another technique, for instance IR-ATR spectroscopy, which allows deducing the order parameter (P4) and (cos2<5). 

In materials investigations surface-sensitive techniques are of special interest. The major contribution of infrared spectroscopy to this field is internal reflection spectroscopy (IRS), often called the "attenuated total reflection" (ATR) technique. To describe theory and principle, electromagnetic wave theory must be apphed [33]. 

Many compounds exhibit near-IR and mid-IR absorption. By using IR transparent optical fibers, detection of an absorption band in the IR region is possible for optical sensing. Both direct sensing using the absorption property of the analyte or indicator sensing are widely exploited. Most mid-IR sensing schemes are based on the principles of internal reflection spectroscopy, or the attenuated total reflection (ATR) [3,14-21],... 

D. Horsley, J. Herron, V. Hlady, and J. D. Andrade, Human and hen lysozyme adsorption A comparative study using total internal reflection fluorescence spectroscopy and molecular graphics, in Proteins at Interfaces Physicochemical and Biochemical Studies (J. L. Brash and T. A. Horbett, eds.), ACS Symposium Series No. 343, pp. 290-305, American Chemical Society, Washington, D.C. (1987). 

V. Hlady, C. Golander, and J. D. Andrade, Hydrophobicity gradient on silica surfaces A study using total internal reflection fluorescence spectroscopy, Colloids Surf. 33, 185-190... 

M. Masuhara, S. Tazuke, N. Tamai, and I. Yamazaki, Time-resolved total internal reflection fluorescence spectroscopy for surface photophysics studies, J. Phys. Chem. 90, 5830-5835 (1986). 

A. Itaya, T. Yamada, K. Tokuda, and H. Masuhara, Interfacial characteristics of poly(methyl methacrylate) film Aggregation of pyrene and micropolarity revealed by time-resolved total internal reflection fluorescence spectroscopy, Polym. J. 22, 697-704 (1990). 

N. L. Thompson, T. P. Burghardt, and D. Axelrod, Measuring surface dynamics of biomolecules by total internal reflection with photobleaching recovery or correlation spectroscopy, Biophys. J. 33, 435-454 (1981). 

Techniques which allow one to monitor the boundary layer as a function of time, such as total internal reflection fluorescence (TIRF) spectroscopy 4 43), permit a quantitative evaluation of interfacial mass transport processes using, for example, fluorescently-tagged macromolecules which do not adsorb, such as fluorescein-labeled dextran 40 ... 

As a rule these methods are based on the concept of evanescent surface waves caused by total internal reflection at a solid/liquid interface. In order to understand the so-called evanescent spectroscopy, a simplified theory of total internal reflection is given below. More complete treatments can be found in various specialized monographs and reviews 145 147>. 

Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy. Attenuated total reflectance (atr) ftir spectroscopy is based on the principle of total internal reflection (40). Methods based on internal reflection in the uv and visible regions of the spectrum are also common in addition to those in the ir region. The implementation of internal reflection in the ir region of the spectrum provides a means of obtaining ir spectra of surfaces or interfaces, thus providing molecularly-specific vibrational information. 

Picosecond time-resolved total internal reflection fluorescence spectroscopy was applied to analyze the proton-transfer reaction of INpOH in water-sapphire interface layers [206], The rate constant of the proton-transfer reaction from excited neutral species became slow in the interface layer as compared with that in the bulk aqueous solution and decreased smoothly with increasing penetration depth in the interfacial layer up to 100 nm. The anomaly was interpreted in terms of rotational fluctuations of water aggregates in the interface layer. 

T. E. Starr and N. L. Thompson, Total internal reflection with fluorescence correlation spectroscopy Combined surface reaction and solution diffusion, Biophys. J. 80, 1575-1584 (2001). 

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