Circular dichroism artifacts

Malon P, Keiderling TA (1988) A solution to the artifact problem in Fourier-transform vibrational circular-dichroism. Appl Spectrosc 42 32-38... 

When chirality is involved, information on solid-state structures and supra-molecular properties must be obtained by solid-state circular dichroism (CDf spectroscopy, as certain characteristics may be lost upon dissolution. However extreme care is required to obtain artifact-free solid-state CD spectra. This is because CD spectra in the solid state (except for special homogeneous cases [9,10]) are inevitably accompanied by parasitic signals that originate from thd macroscopic anisotropies of a sample such as LD (linear dichroism) and LB (linear birefringence) [11-16]. We have been working in the field of solid-state chirality for the last 30 years and recently developed a novel universal chiroptical spectrophotometer, UCS J-800KCM, for the measurement of true CD and circular birefringence (CB) spectra in the solid state [17]. 

The measurement of vibrational optical activity (VOA) lacks some of the severe disadvantages mentioned. Vibrational spectral bands are less likely to overlap and can be measured using two complementary techniques namely infrared and Raman spectroscopy. They can be measured as well in the crystalline as in the liquid or gaseous state, and the techniques are applicable to solutions while nearly reaching (complemented with the appropriate theoretical models) the accurateness of the X-ray method. VOA has drawbacks too the effects are quite small and tend to be obscured by artifacts. They are about 10 times weaker than the optical rotatory dispersion (ORD) and the circular dichroism (CD) in the UV-VIS range. However, this apparent disadvantage is more and more relieved by instrumental advances. 

CD samples must be isotropic, at least in the direction perpendicular to the light path, since linear dichroism (LD, birefringence) causes large distortion of CD spectra. Therefore, samples of solid dispersions, membranes, films, gels, and liquid crystals should be prepared with great care to minimize anisotropy. Furthermore, the measurement of nonsolution samples should be repeated several times after successive rotation of the cell around the light beam axis to check the independency from linear dichroic interference. Some reliable studies show LD data with CD curve in order to examine artifacts. The linear dichroic interference may be too large for solid-state samples, and hence their measurement may require specialized instruments. Chiral liquid crystal (nematic or smectic C phase) exhibits a characteristic circular dichroic phenomenon irrelevant to... 

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