Optical handedness

Circular dichroism(CD) is the differential absorption of left- and right-handed circularly polarized light, due to molecules that have optical handedness or optical activity (this happens for most molecules of biological interest—for example, the a helix, [1 sheet, and random coil regions of proteins and the double helix of nucleic acids have recognizable CD spectral signatures). 

Mixtures containing equal quantities of enantiomers are called racemic mixtures Racemic mixtures are optically inactive Conversely when one enantiomer is present m excess a net rotation of the plane of polarization is observed At the limit where all the molecules are of the same handedness we say the substance is optically pure Optical purity or percent enantiomeric excess is defined as... 

If a molecule is nonsuperimposable on its miixor image, the mirror image must be a different molecule, since superimposability is the same as identity. In each case of optical activity of a pure compound there are two and only two isomers, called enantiomers (sometimes enantiomorphs), which differ in structure only in the left-and right-handedness of their orientations (Fig. 4.1). Enantiomers have identical physical and chemical properties except in two important respects ... 

Accurate experimental determinations require that not only the handedness of the produced light, but its exact degree of polarization, are known. The theoretical performance of an undulator may be in practice be degraded by magnetic defects, and the optical beam can be further depolarized by reflections along the beamline. Again, the dephasing on optical elements can in principle be... 

Ever since the beginning of life on primitive Earth, biopolymers and biomolecules have essentially comprised optically active constituents because of the natural selection of Z-amino acids and tZ-sugars. Although the origin of this biomolecular handedness is a long debated issue among biologists, chemists, physicists, and astronomers,1 5 it is accepted that our life is a consequence of the chemistry of homochiral biosubstances. Deoxyribonucleic acid (DNA) is a classic example of a chiral biopolymer. Its chirality is essentially characterized... 

From the diameter of the disclinations, the pitch can be measured30 furthermore, clockwise rotation of the lens generates a shrinking or an expansion of the circles, according to the cholesteric handedness from this, the helical handedness can be deduced.31 It should be stressed that this is not a spectroscopic method and gives results completely independent from those obtained with CD or optical rotation. 

Films of pure CNLCs have a unique transmission behavior as CP light with the same sense of circular polarization as the CNLC is filtered out by reflection, while CP light of the opposite handedness as the CNLC film is transmitted. This selective optical transmission characteristic is referred to as a one-dimensional photonic stop-band or a selective reflection band. The stop-band is centered at a certain wavelength Ac, which is dependent on the pitch length p and the average refractive index n of the CNLC ... 

Molecules which exhibit optical activity are molecules which have a handedness in their structure. They are chiral . Chemists often have reasons to obtain chemical pure aliquots of particular molecules. Since the chirality of molecules can influence biological effect in pharmaceuticals, the chiral purity of a drug substance can pose a challenge both in terms of obtaining the molecules and in assaying the chiral purity by instrumental methods. While diastereomers can have different physical properties including solubility, enantiomers have the same physical properties and the same chemical composition. How then to separate optically active molecules ... 

The inactivity in the molecule is due to the fact that it is perfectly symmetric as shown by the dotted line, the upper half exactly coinciding with the lower half. Therefore, molecular asymmetry and not the presence of asymmetric carbon atoms is responsible for optical activity. Since the term asymmetric has been found to be inadequate, now the term chirality has been introduced. The word chiral (the Greek word cheir means hand pronounced kiral) signifies, the property of Handedness . An object that in not superimposable upon its mirror image is chiral and this mirror-image relationship is the same as left hand has with the right. If an object and its mirror image can be made to coincide in space, they are said to be achiral. 

What are the facts of life One of the most striking is that all known living systems involve the same types of polymers, i.e., three varieties of homochiral biopolymers. That is, each variety is composed of unique molecular building blocks having the same three-dimensional handedness. Thus, with rare exceptions, the proteins found in cells are composed exclusively of the 1-enantiomers of 19 optically active amino acids (Fig. 11.1). Similarly, only D-ribose and 2-deoxy-D-ribose sugars are found in the nucleic acid polymers that make up the RNAs and DNAs, which are essential for protein synthesis in the cell and for the transmission of genetic information from one generation to the next. 

Werbowyj and Gray (79) examined the relationships between the cholesteric pitch and optical properties of HPC in water, CH3COOH and CH3OH. The reciproc pitch varied as the third power of the HPC concentration. Optical rotatory dispersion results show HPC has a right-handed superhelicoidal structure regardless of structure. As will be discussea below, a change in solvent can reverse the handedness of other cellulose derivatives. 

Fig. 21 Spiral structiu-e formed by seven beam interference central beam is right-handed circularly polarized, and the side beams linearly [32,33]. Simulated by interference of plane waves according to Eq. 2 with side beams comprising an 80° angle with the optical axis (the -field of the central beam is Eo = o/V2(l, i,0), where + corresponds to the right-handedness i = V )...

In older literature optical isomerism of the type represented by d and l pairs was usually discussed in terms of "asymmetric carbon atoms" or "asymmetric centers." Now the terms chiral (pronounced ki-ral) molecules, chiral centers, and chirality (Greek "handedness") are preferred. 

Molecules of inheient structural asymmetry aie anisotropic they are optically active and exhibit optical rotation in solution. The typical optically active center is a carbon atom with four different substituents. In addition, any structural dissymmetry that results in a spatial left- and right-handedness will cause optical activity. Compounds of these types of come in a right-hand l R) and left-hand (L) form. When equal amounts of these two forms are mixed (racemic mixtures) there is no optical rotation because the activity of the two forms exactly cancel. Internal compensation of optically active centers m complex molecules is also found. Left- and right-handed optical isomers were first studied by Pasteur well over 100 years ago. and extensive surveys are found in most organic chemical texts. 

Inorganic complexes. Molecules that can support optical activity are said to be chiral, and to possess chirality (meaning handedness, since the human hand is chiral). 

That both phenomena arise as a consequence of macroscopic solvent order and not Intimate solvent-solute Interactions Is clear Saeva and 01In (75) have shown that solute LCICD spectra can be observed In twisted nematic phases only Nakazaki et al. (76) find an excess of one enantiomer of hexahelicene Is produced photochemlcally from achiral precursors In twisted nematic phases no LCICD spectra or optical Induction occurs In untwisted nematic phases and the handedness of the twist can be correlated with the sign of the LCICD and the preferred product enantiomer. Furthermore, Isotropic phases of cholesteric mixtures display no discernible LCICD spectra (12, 67) and the enantiomeric excesses In products of photolablle reactants In Isotropic phases are near zero (51). 

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