Polarized light production

W. A. Shurcliff, Polarized Light production and use , Oxford Univ. Press,... 

W. A. Shurcliff (1962). Polarized Light Production and Use (Harvard University Press, Cambridge, MA). 

At 321 mn there is a vibronic origin marked This has one quantum of v, the antisynnnetric C-H stretching mode, in the upper state. Its intensity is induced by a distortion along This state has B2 vibrational symmetry. The direct product of B2 and A2 is B, so it has B vibronic syimnetry and absorbs x-polarized light. One can also see a 4 6,, vibronic origin which has the same syimnetry and intensity induced by... 

This concept has been known for over a century. Expressed as Brewster s Constant law, it states that the index of refraction in a strained material becomes directional, and the change of the index is proportional to the magnitude of the stress (or strain) present. Therefore, a polarized beam in the clear plastic splits into two wave fronts in the X and Y directions that contain vibrations oriented along the directions of principal stresses. An analyzing filter passes only vibrations parallel to its own transmitting plane (Chapter 4, TRANSPARENT AND OPTICAL PRODUCT, Polarized Lighting). 

There is the microtoming optical analysis test. In this procedure thin slices (under 30 tixri) of the plastics are cut from the product at any level and microscopically examined under polarized light transmitted through the sample. Rapid quality and failure analysis examination occurs by this technique. This technique has been used for many years in biological studies and by metallurgists to determine flaws, physical and mechanical properties. Examination can be related to stress patterns, mechanical properties, etc. 

As the story goes, a wine production batch gone bad provided fairly large amounts of a new organic compound, the study of which was deemed of practical importance for the French wine industry. The new material had the same molecular formula as tartaric acid, which to some experts of the time meant it had to be the same as tartaric acid. Solutions of salts of the new material, however, did not rotate the plane of polarization of plane-polarized light, as solutions of salts of tartaric acid were known to do. The new material was named para tartaric acid, or racemic acid (the name racemic acid being derived from the Latin racemus bunch of grapes). 

When following the (dual-route) reaction of a secondary halide with hydroxide ion, we find that the angle 9 through which plane polarized light is rotated will decrease, as for primary and tertiary halides, but will not reach zero at completion. In fact, the final angle will have a value between 0° and 6>finai because of the mixtures of products, itself a function of the mixture of SnI and Sn2 reaction pathways. 

The concept of transition moment is of major importance for all experiments carried out with polarized light (in particular for fluorescence polarization experiments, see Chapter 5). In most cases, the transition moment can be drawn as a vector in the coordinate system defined by the location of the nuclei of the atoms4 therefore, the molecules whose absorption transition moments are parallel to the electric vector of a linearly polarized incident light are preferentially excited. The probability of excitation is proportional to the square of the scalar product of the transition moment and the electric vector. This probability is thus maximum when the two vectors are parallel and zero when they are perpendicular. 

Since the early times of stereochemistry, the phenomena related to chirality ( dis-symetrie moleculaire, as originally stated by Pasteur) have been treated or referred to as enantiomericaUy pure compounds. For a long time the measurement of specific rotations has been the only tool to evaluate the enantiomer distribution of an enantioimpure sample hence the expressions optical purity and optical antipodes. The usefulness of chiral assistance (natural products, circularly polarized light, etc.) for the preparation of optically active compounds, by either resolution or asymmetric synthesis, has been recognized by Pasteur, Le Bel, and van t Hoff. The first chiral auxiliaries selected for asymmetric synthesis were alkaloids such as quinine or some terpenes. Natural products with several asymmetric centers are usually enantiopure or close to 100% ee. With the necessity to devise new routes to enantiopure compounds, many simple or complex auxiliaries have been prepared from natural products or from resolved materials. Often the authors tried to get the highest enantiomeric excess values possible for the chiral auxiliaries before using them for asymmetric reactions. When a chiral reagent or catalyst could not be prepared enantiomericaUy pure, the enantiomeric excess (ee) of the product was assumed to be a minimum value or was corrected by the ee of the chiral auxiliary. The experimental data measured by polarimetry or spectroscopic methods are conveniently expressed by enantiomeric excess and enantiomeric... 

Enantiomers have very similar chemical properties, but they rotate polarized light in opposite directions (optical activity, see pp. 36,58). The same applies to the enantiomers of lactic acid. The dextrorotatory L-lactic acid occurs in animal muscle and blood, while the D form produced by microorganisms is found in milk products, for example (see p.l48). The Fischer projection is often used to represent the formulas for chiral centers (cf.p. 58). 

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