Infrared absorption spectra dichroism

Although Lowry iu his classical treatise in 1935 discussed the possibility of detection of circular dichroism arising from molecular vibration transitions, only in the past two decades has it been possible to measure optical activity associated with infrared absorption transitions, CD maxima first being detected in the VCD spectrum for the C—H stretching modes of the enantiomers of 2,2,2-trifluoro-l-phenylethanol as the neat liqnid . This work was initiated with the view that such measurements would eventually yield information concerning absolute configurations and molecular conformations of... 

Fig. 11.9 Typical absorbance spectrum of a mesogenic compound (in the isotropic phase) with absorption bands in the visible and infrared spectra (a), typical molecular moieties responsible for the UV and IR absorption (b) and characteristic polarization absorption spectra (dichroism) in the nematic phase (c)...

Although a transmittance IR absorption spectrum measurement evaluates the bulk of the alignment material, the distribution of the alignment of the molecules can he determined hy a qualitative analysis by changing the polar and azimuthal angles of the sample. The relationship between the dichroism of the polyimide and its thickness was studied using polarized infrared absorption measurements, and it was found that the dichroism was consistently less than 17 nm and decreased when the polyimide becomes thicker [22]. From these results and retardation measurements, a molecular distribution model was proposed which shows uniform anisotropy to some depth, lower anisotropy in deeper areas, and isotropy in areas which are even deeper [22]. 

The mass of histone in the chromosomes is larger than that necessary purely for structures of this type, as shown in Fig. 85. Considering the total mass of histone in the chromosomes, these workers conclude from the absence of orientation of the diffraction spectrum and the absence of dichroism of infrared absorption of histone that the polypeptide chain of histones is not all arranged in the same way, along or perpendicular to the length of the DNA molecules. 

The absorption modes of (S)-3-phenyl-2-hydroxypropionic acid, (S)-3-phenyl-2-aminopropionic acid, and (S)-alanine adsorbed on a nickel plate or RNi were studied by Suetaka s group (71, 72). From the measurement of infrared (IR) dichroism in the reflection spectrum, the molecular orientation of the modifying reagent was deduced. Figures 19-21 show molecular orientations of (S)-2-hydroxy-3-phenylpropionic acid on a nickel plate and (R)-alanines on RNis modified at 5° and 100°C, respectively. 

Figure 23-3 Infrared absorbance spectra of the amide regions of proteins. (A) Spectra of insulin fibrils illustrating dichroism. Solid line, electric vector parallel to fibril axis broken line, electric vector perpendicular to fibril axis. From Burke and Rougvie.24 Courtesy of Malcolm Rougvie. See also Box 29-E. (B) Fourier transform infrared (FTIR) spectra of two soluble proteins in aqueous solution obtained after subtraction of the background H20 absorption. The spectrum of myoglobin, a predominantly a-helical protein, is shown as a continuous line. That of concanavalin A, a predominantly (3-sheet containing protein, is shown as a broken line. From Haris and Chapman.14 Courtesy of Dennis Chapman.

Figure 4.6-5 Infrared linear dichroism of a nematic sample (EBBA/MBBA equimolar mixture of N-(p-ethoxybenzylidene)-//- -butylaniline and its methoxy analogue 2 of Table 4.6-1 Riedel-de Haen) expressed as the difference of the absorption indices k and ke (imaginary part of the complex refractive index) for the ordinary and the extraordinary beam, resp. the temperature increases and thus, the degree of order decreases from spectrum a to spectrum d, the latter was taken close to the clearing point F, where the order and consequently the anisotropy vanishes (Reins et al., 1993).

Chemical compounds absorb infrared radiation when there is a dipole moment change (in direction and/or magnitude) during a molecular vibration, molecular rotation, or molecular rotation-vibration. Absorptions are also observed with combinations, differences or overtones of molecular vibrations. A specific type of molecule is limited in the number of vibrations and rotations it is allowed to undergo. Therefore, each chemical compound has its own specific set of absorption frequencies and thus exhibits its own characteristic IR spectrum. This unique property of a compound allows the organic chemist to identify and quantify an unknown sample. (A special infrared technique called vibrational circular dichroism (VCD) is required to distinguish optical isomers). 

Vibrational circular dichroism (VCD) is defined as circular dichroism (CD) in vibrational transitions in molecules. These transitions typically occur in the infrared (IR) region of the spectrum and hence a VCD spectrometer is an infrared spectrometer that can measure the circular dichroism associated with infrared vibrational absorption bands. CD is defined as the difference in the absorption of a sample for left versus right circularly polarized radiation. This difference is zero unless the sample possesses molecular chirality, either through its constituent chiral molecules or through a chiral spatial arrangement of non-chiral molecules. 

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