Optical rotation dispersive effects

From another point of view MCD can be regarded as the absorptive counterpart of magnetic optical rotation dispersion (MORD) the well-known Faraday effect. This is the reason why in the past the spectra were given in the units of natural optical rotation per magnetic field... 

Faraday found experimentally that all substances show this effect in presence of a magnetic field (Schatz and Me Caffery, 1969), leading to Magnetic optical rotation dispersion (MORD) and Magnetic circular dichroism (MCD) (Caldwell and Eyring, 1976 Dawber, 1964 Foss and Mccarvil, 1965 Schatz et al., 1978 Thome, 1977). Experimentally however, ORD and MORD were never measured extensively contrary to CD and MCD. 

It is well known that the CD is always accompanied by an optical rotation dispersion (Cotton effect). Such a Cotton effect has also been observed [108]. It is clear that a helically arranged system of emitting molecules should exhibit also a fluorescence circular dichroism. Such an effect has been reported very recently [110]. 

Enantiomers can be distinguished by their rotation of plane-polarized light at a specific wavelength, or over a range of wavelengths (optical rotatory dispersion, ORD), as well as by the difference in absorption of right and left circularly polarized light (circular dichroism. Cotton effect, CD). 

Rotation of the polarization plane (or the axes of the dichroic ellipse) by a small angle a occurs when the phases for the two circular components become different, which requires a difference in the refractive index n (Pearlman and Nguyen 1991). This effect is called circular birefringence. The change of optical rotation with wavelength is called optical rotary dispersion (ORD). 

In 1892, Biot confirmed that the colors on propagating white light parallel to the optical axis of a quartz crystal placed between crossed polarizers arise from two distinct effects, the rotation of the plane of polarization of monochromatic light and dispersion of the rotation with respect to wavelength. Biot s discovery was extended to the optical rotation of natural products in solution or in the liquid phase, and this is of chemical significance, as it indicates that rotation is a molecular effect. 

Optical rotatory dispersion involves measuring the variation of optical rotation with wavelength. There is an abrupt reversal of rotation in the vicinity of an absorp- tion band. If the complex is initially levorotatory (Fig. 12.25a), the ORD curve fells to a minimum, rises rapidly to a maximum, and then slowly falls. If the complex was initially dextrorotatory, the effect is reversed with the ORD curve rising first to a ... 

The most commonly encountered manifestations of chiroptical phenomena are circular birefringence (also known as optical rotation), optical rotatory dispersion (ORD), and circular dichroism (CD). An explanation as to the nature of circularly and linearly polarized light is provided, and the origins of the various chiroptical effects are discussed. In each instance, a concise summary of the calculations used by workers in the field to report the results of their investigations is provided. 

The interaction of polarized light with chiral compounds is of great interest since chiroptical techniques are extremely useful as methods of characterization. It is equally true that although most scientists are aware that enantiomerically rich solutions will rotate the plane of linearly polarized light, the origins of this effect are not as simple as might be imagined. In this first article, the phenomena of polarimetry and optical rotatory dispersion will be discussed. A subsequent note will concern the related phenomenon of circular dichroism. 

ABA absorbs ultraviolet with maxima at 240 nm (e 2.1 x 104, a shoulder peak), 260 nm (e 2.6 x 104), and 320 nm (e 50) in an acidic methanol solution.590 Irradiation with UV with a wavelength shorter than 305 nm isomerizes the 2-(Z)-double bond to (E) to give an equilibrium mixture of ABA and its 2-( )-isomer with a ratio of 1 1, and also causes decomposition of ABA to unidentified compounds by the excitation of the 7t-7t transition of the side chain and the enone groups. ABA has a strong optical activity, and its specific optical rotation is +430° in an acidic methanol solution.591 In the optical rotatory dispersion (ORD)591 and the circular dichroism (CD) spectra,558 ABA shows a positive Cotton effect from 300 to 200 nm. Phaseic acid and dihydrophaseic acid and its epimer, which did not have the enone group, show a small specific optical rotation with a minus value and also a negative plain curve in the ORD. 

Palytoxin is a white, amorphous, hydroscopic solid that has not yet been crystallized. It is insoluble in nonpolar solvents such as chlorophorm, ether, and acetone sparingly soluble in methanol and ethanol and soluble in pyridine, dimethyl sulfoxide, and water. The partition coefficient for the distribution of palytoxin between 1-butanol and water is 0.21 at 25°C based on comparison of the absorbance at 263 nm for the two layers. In aqueous solutions, palytoxin foams on agitation, like a steroidal saponin, probably because of its amphipathic nature. The toxin shows no definite melting point and is resistant to heat but chars at 300°C. It is an optically active compound, having a specific rotation of -i-26° 2° in water. The optical rotatory dispersion curve of palytoxin exhibits a positive Cotton effect with [a]25o being -i-700° and [a]2,j being +600° (Moore and Scheuer 1971 Tan and Lau 2000). 

---