IRRAS spectroscopy

Fig. 37. Schematic comparison between ATR-IR and IR reflection absorption (IRRAS) spectroscopy. In IRRAS, the sample (e.g., an electrode) is typically metallic and reflects the incident IR radiation. The IR beam has to pass through a liquid film twice.

This example demonstrates that quantitative PM IRRAS spectroscopy is a powerful tool to study the potential-driven transformation of a phospholipid bi-... 

The interactions of PABA with RNA were investigated with UV-Vis and PM-IRRAS spectroscopy. Figure 3.33 shows the absorption spectra of a PABA layer (both salt and base form) and a PABA/RNA bilayer. The layer of PABA in the salt form (Figure 3.33, a) exhibits the characteristic absorption bands around 400 and 800 nm attributed to tt-tt and bipolaron band transitions, respectively [53, 54]. The blue shift in the bipolaron band of the base form of the PABA layer (Figure 3.33, b) from 800 to 740 nm was observed upon exposure to PBS at pH 7.4 because of the removal of D-fructose and fluoride [37]. Subsequent complexation of the PABA layer in its base form with RNA resulted in a red shift in the bipolaron band from 740 to 800 nm, together with a small increase in the absorbance. These results reportedly confirmed the complexation of RNA with PABA under neutral conditions by the formation of the bilayer through anionic boronate esters, and subsequent conversion of the base form of PABA back to a self-doped salt form. The creation of the anionic tetrahedral boron forms the basis of multilayer formation. Further, the formation of boronate esters and a boron-nitrogen dative bond, as well as electrostatic interactions of anionic phosphates with cationic amines is supported by PM-IRRAS spectroscopy. After complexation... 

IRRAS spectroscopy indicates that the quarterthiophene is almost parallel to the surface normal [134,135] while the terthiophene-aUcanethiol 17 is tilted about 14° away from the surface normal [136]. 

The reconstitution reaction of heme derivatives with apo-protein on gold surfaces is a convenient method for fabricating well-ordered protein mono-layers on solid substrates as a first step for the structural analysis of proteins and also for device applications. Kobayashi and coworkers synthesised thi-olated heme compounds to investigate the self-assembly behaviour on gold (Fig. 22) [119,168]. UV- and IRRAS-spectroscopy indicate that the tilt angle of the adsorbed molecules depends on the alkyl chain length between the surface and the chromophore. 

Russell et al. synthesised a series of phthalocyanine alkanethiols and disulfides with different length of alkyl spacers (Fig. 23). IRRAS spectroscopy indicates that the orientation of the phthalocyanine macrocycles towards the gold... 

Merocyanines are widely used as solvatochromic dyes. Fujita et al. demonstrated that the Brooker s dye analogue (Fig. 32, 24) shows a colour change based on protonation and deprotonation in a densely packed SAM (Fig. 32, 24) [196]. Surface plasmon spectroscopy and X-ray photoelectron spectroscopy indicate that the monolayers are closely packed. The layer thickness is consistent with the molecules having a tUt angle of 30° to the surface normal IRRAS spectroscopy shows that the chromophores are located in a polar local dielectric situation even in non-polar solvents. Nonetheless, the deprotonated, zwitterionic form of the dye shows a distinct negative solva-tochromism depending on the solvent polarity. 

Giasson, S., Palermoa, T., Buffeteau, T., Desbat B. and Turlet, J. M., Study of boundary film formation with overbased calcium sulfonate by PM-IRRAS spectroscopy. Thin Solid Films, 252, 1994, 111-119. 

Recent work in our laboratory has shown that Fourier Transform Infrared Reflection Absorption Spectroscopy (FT-IRRAS) can be used routinely to measure vibrational spectra of a monolayer on a low area metal surface. To achieve sensitivity and resolution, a pseudo-double beam, polarization modulation technique was integrated into the FT-IR experiment. We have shown applicability of FT-IRRAS to spectral measurements of surface adsorbates in the presence of a surrounding infrared absorbing gas or liquid as well as measurements in the UHV. We now show progress toward situ measurement of thermal and hydration induced conformational changes of adsorbate structure. The design of the cell and some preliminary measurements will be discussed. 

K. and Enyo, M. (1989) Surface species produced on Pt electrodes during HCHO oxidation in sulfuric add solution as studied by infrared reflection-absorption spectroscopy (IRRAS) and differential electrochemical mass spectroscopy (OEMS)./. Electroanal. Chem., 258, 219-225. 

The three most commonly applied external reflectance techniques can be considered in terms of the means employed to overcome the sensitivity problem. Both electrically modulated infrared spectroscopy (EMIRS) and in situ FTIR use potential modulation while polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) takes advantage of the surface selection rule to enhance surface sensitivity. 

Polarisation modulation infrared rejiection-absorption spectroscopy (PM-IRRAS or JRRAS). Potential modulation IR studies rely on switching the potential at a reflective electrode between rest and active states, generating difference spectra. However, the EMIRS technique has several drawbacks the relatively fast potential modulation requires that only fast and reversible electrochemical process are investigated the absorption due to irreversibly chemisorbed species would be gradually eliminated by the rapid perturbation. Secondly, there is some concern that rapid modulation between two potentials may, to some extent, in itself induce reactions to occur. 

Electrochemical infrared spectroscopy can be used on all kinds of electrodes and for all substances that are IR active. It is particularly useful for the identification of reaction intermediates, and has been used extensively for the elucidation of the mechanisms of technologically important reactions. A case in point is the oxidation of methanol on platinum, where linearly bonded = C = O (i.e., CO bonded to one Pt atom) has been identified as an intermediate Figs. 15.7 and 15.8 show EMIRS [6c] and IRRAS [8] spectra of this species. Near 2070 cm-1 the EMIRS spectrum shows the typical form produced by a peak that shifts with potential. This shift can be followed in the IRRAS spectrum... 

Some characteristics of, and comparisons between, surface-enhanced Raman spectroscopy (SERS) and infrared reflection-absorption spectroscopy (IRRAS) for examining reactive as well as stable electrochemical adsorbates are illustrated by means of selected recent results from our laboratory. The differences in vibrational selection rules for surface Raman and infrared spectroscopy are discussed for the case of azide adsorbed on silver, and used to distinguish between "flat" and "end-on" surface orientations. Vibrational band intensity-coverage relationships are briefly considered for some other systems that are unlikely to involve coverage-induced reorientation. 

SERS) (1) and several variants of infrared reflection-absorption spectroscopy (IRRAS) (2). ... 

The combination of surface enhanced Raman scattering (SERS) and infrared reflection absorption spectroscopy (IRRAS) provides an effective in-situ approach for studying the electrode-electrolyte interface. The extreme sensitivity to surface species of SERS is well known. By using polarization modulation of the infrared beam for IRRAS, the complete band shape is obtained without modulating the electrode potential. 

Infrared drying, ceramics processing, 5 656 Infrared dyes, 9 500 Infrared emission spectroscopy, 23 142 Infrared inks, 14 315 Infrared lasers, 22 180 Infrared LEDs, 22 175, 176 Infrared measurements, in growing amorphous silicon, 22 130 Infrared microspectroscopy, 16 486 Infrared reflection-absorption spectroscopy (irras), 24 72, 114-116. See also IR spectra... 

Ir spectra, of surface layers, 24 110. See also Infrared reflection-absorption spectroscopy (IRRAS) ir spectrometers, 23 132 Ir (infrared) spectroscopy, for analysis of MF resins, 15 790. See also Infrared technology Isanic acid, 5 34t... 

PM-IRRAS Polarization-modulated infrared reflertion absorption specTroscopy... 

Most of the above membrane-oriented studies were carried out for peptides in multilayer systems that were collapsed or transferred onto a sample cell surface. An alternative and very interesting way to study membrane systems is by IRRAS (infrared reflection absorption spectroscopy) at the air-water interface. In this way, unilamellar systems can be studied as a function of surface pressure and under the influence of various membrane proteins and peptides added. Mendelsohn et al.[136] have studied a model series of peptides, [K2(LA) ] (n = 6, 8, 10, 12), in nonaqueous (solution), multilamellar (lipid), and unilamellar (peptide-IRRAS) conditions. In the multilamellar vesicles these peptides are predominantly helical in conformation, but as peptide only monolayers on a D20 subphase the conformation is (1-sheet like, at least initially. For different lengths, the peptides show variable surface pressure sensitivity to development of some helical component. These authors further use their IR data to hypothesize the existence of the less-usual parallel (i-sheet conformation in these peptides. A critical comparison is available for different secondary structures as detected using the IRRAS data for peptides on H20 and D20 subphasesJ137 ... 

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