Optical rotation, also known as polarization rotation or circular birefringence, is the rotation of the orientation of the plane of polarization about the optical axis of linearly polarized light as it travels through certain materials. Circular birefringence and circular dichroism are the manifestations of optical activity. Optical activity occurs only in chiral materials, those lacking microscopic mirror symmetry. Unlike other sources of birefringence which alter a beam's state of polarization, optical activity can be observed in fluids. This can include gases or solutions of chiral molecules such as sugars, molecules with helical secondary structure such as some proteins, and also chiral liquid crystals. It can also be observed in chiral solids such as certain crystals with a rotation between adjacent crystal planes (such as quartz) or metamaterials.
When looking at the source of light, the rotation of the plane of polarization may be either to the right (dextrorotatory or dextrorotary — d-rotary, represented by (+), clockwise), or to the left (levorotatory or levorotary — l-rotary, represented by (−), counter-clockwise) depending on which stereoisomer is dominant. For instance, sucrose and camphor are d-rotary whereas cholesterol is l-rotary. For a given substance, the angle by which the polarization of light of a specified wavelength is rotated is proportional to the path length through the material and (for a solution) proportional to its concentration.
Optical activity is measured using a polarized source and polarimeter. This is a tool particularly used in the sugar industry to measure the sugar concentration of syrup, and generally in chemistry to measure the concentration or enantiomeric ratio of chiral molecules in solution. Modulation of a liquid crystal's optical activity, viewed between two sheet polarizers, is the principle of operation of liquid-crystal displays (used in most modern televisions and computer monitors).
Forms
Dextrorotation and laevorotation (also spelled levorotation)The first word component dextro- comes from the Latin word dexter, meaning "right" (as opposed to left). Laevo- or levo- comes from the Latin laevus, meaning "left side".The equivalent French terms are dextrogyre and lévogyre. These are used infrequently in English, but sometimes they are, see e.g. Patrick Mailliet et al., page 12 and 15. in chemistry and physics are the optical rotation of plane-polarized light. From the point of view of the observer, dextrorotation refers to clockwise or right-handed rotation, and laevorotation refers to counterclockwise or left-handed rotation.LibreTexts Chemistry – Polarimetry
A chemical compound that causes dextrorotation is dextrorotatory or dextrorotary, while a compound that causes laevorotation is laevorotatory or laevorotary. Compounds with these properties consist of chiral molecules and are said to have optical activity. If a chiral molecule is dextrorotary, its enantiomer (geometric mirror image) will be laevorotary, and vice versa. Enantiomers rotate plane-polarized light the same number of degrees, but in opposite directions.
Chirality prefixes
A compound may be labeled as dextrorotary by using the "(+)-" or "d-" prefix. Likewise, a levorotary compound may be labeled using the "(−)-" or "l-" prefix. The International Union of Pure and Applied Chemistry, the authority on chemical nomenclature, strongly discourages use of the "d-" and "l-" prefixes. The lowercase "d-" and "l-" prefixes are distinct from the SMALL CAPS "D-" and "L-" prefixes. The "D-" and "L-" prefixes are used to specify the enantiomer of chiral organic compounds in biochemistry and are based on the compound's absolute configuration relative to (+)-glyceraldehyde, which is the D-form by definition.
The prefix used to indicate absolute configuration is not directly related to the (+) or (−) prefix used to indicate optical rotation in the same molecule. For example, nine of the nineteen L-amino acids naturally occurring in proteins are, despite the L- prefix, actually dextrorotary (at a wavelength of 589 nm), and D-fructose is sometimes called "levulose" because it is levorotary. The two naming systems can be combined to indicate both absolute configuration and optical rotation, as in D-(+)-glyceraldehyde.
The D- and L- prefixes describe the molecule as a whole, as do the (+) and (−) prefixes for optical rotation. In contrast, the (R)- and (S)- prefixes from the Cahn–Ingold–Prelog priority rules characterize the absolute configuration of each specific chiral stereocenter with the molecule, rather than a property of the molecule as a whole. A molecule having exactly one chiral stereocenter (usually an asymmetric carbon atom) can be labeled (R) or (S), but a molecule having multiple stereocenters needs more than one label. For example, the essential amino acid L-threonine contains two chiral stereocenters and is written (2S,3S)-threonine. There is no strict relationship between the R/S, the D/L, and (+)/(−) designations, although some correlations exist. For example, of the naturally occurring amino acids, all are L, and most are (S). For some molecules the (R)-enantiomer is the dextrorotary (+) enantiomer, and in other cases it is the levorotary (−) enantiomer. The relationship must be determined on a case-by-case basis with experimental measurements or detailed computer modeling.See, for example,
History
The rotation of the orientation of linearly polarized light was first observed in 1811 in quartz by French physicist François Arago.Arago (1811) "Mémoire sur une modification remarquable qu'éprouvent les rayons lumineux dans leur passage à travers certains corps diaphanes et sur quelques autres nouveaux phénomènes d'optique" (Memoir on a remarkable modification that light rays experience during their passage through certain translucent substances and on some other new optical phenomena), Mémoires de la classe des sciences mathématiques et physiques de l'Institut Impérial de France, 1st part : 93–134. In 1820, the English astronomer Sir John F.W. Herschel discovered that different individual quartz crystals, whose crystalline structures are mirror images of each other (see illustration), rotate linear polarization by equal amounts but in opposite directions.Herschel, J.F.W. (1820) "On the rotation impressed by plates of rock crystal on the planes of polarization of the rays of light, as connected with certain peculiarities in its crystallization," Transactions of the Cambridge Philosophical Society, 1 : 43–51. Jean Baptiste Biot also observed the rotation of the axis of polarization in certain liquidsBiot, J. B. (1815) "Phenomene de polarisation successive, observés dans des fluides homogenes" (Phenomenon of successive polarization, observed in homogeneous fluids), Bulletin des Sciences, par la Société Philomatique de Paris, 190–192. and vapors of organic substances such as turpentine.Biot (1818 & 1819) "Extrait d'un mémoire sur les rotations que certaines substances impriment aux axes de polarisation des rayons lumineux" (Extract from a memoir on the [optical] rotations that certain substances impress on the axes of polarization of light rays), Annales de Chimie et de Physique, 2nd series, 9 : 372–389; 10 : 63–81; for Biot's experiments with turpentine vapor (vapeur d'essence de térébenthine), see pp. 72–81. In 1822, Augustin-Jean Fresnel found that optical rotation could be explained as a species of birefringence: whereas previously known cases of birefringence were due to the different speeds of light polarized in two perpendicular planes, optical rotation was due to the different speeds of right-hand and left-hand circularly polarized light.A. Fresnel, "Mémoire sur la double réfraction que les rayons lumineux éprouvent en traversant les aiguilles de cristal de roche suivant les directions parallèles à l'axe", read 9 December 1822; printed in H. de Senarmont, E. Verdet, and L. Fresnel (eds.), Oeuvres complètes d'Augustin Fresnel, vol. 1 (1866), pp.731–751; translated as "Memoir on the double refraction that light rays undergo in traversing the needles of quartz in the directions parallel to the axis", , 2021 (open access); especially §13. Simple polarimeters have been used since this time to measure the concentrations of simple sugars, such as glucose, in solution. In fact one name for D-glucose (the biological isomer), is dextrose, referring to the fact that it causes linearly polarized light to rotate to the right or dexter side. In a similar manner, levulose, more commonly known as fructose, causes the plane of polarization to rotate to the left. Fructose is even more strongly levorotatory than glucose is dextrorotatory. Invert sugar syrup, commercially formed by the hydrolysis of sucrose syrup to a mixture of the component simple sugars, fructose, and glucose, gets its name from the fact that the conversion causes the direction of rotation to "invert" from right to left.
In 1849, Louis Pasteur resolved a problem concerning the nature of tartaric acid.Pasteur, L. (1850) "Recherches sur les propriétés spécifiques des deux acides qui composent l'acide racémique" (Researches on the specific properties of the two acids that compose the racemic acid), Annales de chimie et de physique, 3rd series, 28 : 56–99; see also appendix, pp. 99–117. A solution of this compound derived from living things (to be specific, wine lees) rotates the plane of polarization of light passing through it, but tartaric acid derived by chemical synthesis has no such effect, even though its reactions are identical and its elemental composition is the same. Pasteur noticed that crystals of this compound come in two asymmetric forms that are mirror images of one another. Sorting the crystals by hand gave two forms of the compound: Solutions of one form rotate polarized light clockwise, while the other form rotate light counterclockwise. An equal mix of the two has no polarizing effect on light. Pasteur deduced that the molecule in question is asymmetric and could exist in two different forms that resemble one another as would left- and right-hand gloves, and that the organic form of the compound consists of purely the one type.
In 1874, Jacobus Henricus van 't Hoffvan 't Hoff, J.H. (1874) "Sur les formules de structure dans l'espace" (On structural formulas in space), Archives Néerlandaises des Sciences Exactes et Naturelles, 9 : 445–454. and Joseph Achille Le BelLe Bel, J.-A. (1874) "Sur les relations qui existent entre les formules atomiques des corps organiques et le pouvoir rotatoire de leurs dissolutions" (On the relations that exist between the atomic formulas of organic substances and the rotatory power of their solutions), Bulletin de la Société Chimique de Paris, 22 : 337–347. independently proposed that this phenomenon of optical activity in carbon compounds could be explained by assuming that the 4 saturated chemical bonds between carbon atoms and their neighbors are directed towards the corners of a regular tetrahedron. If the 4 neighbors are all different, then there are two possible orderings of the neighbors around the tetrahedron, which will be mirror images of each other. This led to a better understanding of the three-dimensional nature of molecules. Note: In accordance with this theory, because there are two asymmetric carbon centers in tartaric acid, there is a third meso form, which has no optical activity. See the tartaric acid article for more.