Polarimetry

Hans Xavier E. Reyes

Part-Time Instructor
ISOMERISM
 Existence of molecule having the same amount
of atoms and chemical formula but different in
many aspects.
◦ Number of bonds
◦ Structural arrangement
◦ Spatial arrangement
Structural/Constitutional Isomerism
 Molecules having the same chemical formula
but different arrangement of the order in which
each atom are connect.
 E.i. C5H12
Sterioisomers/ Spatial isomers
 Same molecular formula, same structural
formula but varying spatial arrangement.
Diasteriomers
 Not related as mirror image or superimposable
pair.
 With two or more stereocenters
 Cis- and Trans-
Enantiomer
 Two stereoisomers that are non-superimposable
image of each other.
 Aka optical isomer, antipode, or optical
antipode
 Basis of polarimetry – dextrorotatory or
levorotatory.
Fischer Projection
 Theoretical means of determining the how a
substance rotates a plane polarized light and
determine the identity of that substance.
Fischer Projection
 The carbon chain is written vertically with the
carbonyl group at the top.
 Identify the carbon containing four different
groups or the chiral carbon.
 If the –OH group is on the left, the isomer is
assigned L- (remember L for Left),
 If on the right, it is assigned D-.
Fischer Projection
The Cahn-Ingold-Prelog rules
 Assigns a molecule’s R and S configuration.
 Based on the decreasing atomic number of the
sidechains of a chiral carbon.
 Does not relate to specific rotation of polar
light.
Chirality and Drugs
 56% of marketed drugs are chiral
 50% are mixtures of enantiomers
 Single-enantiomer formulations of (S)-albuterol,
a β2-adrenergic receptor agonist for treatment
of asthma
 (S)-omeprazole, a proton pump inhibitor for
treatment of gastroesophageal reflux
 (−)-enantiomer of sotalol has both β-blocker
and antiarrhythmic activity,
 (+)-enantiomer has antiarrhythmic properties
but lacks β-adrenergic antagonism.
 The R-enantiomer of fluoxetine, at its highest
administered dose, led to statistically significant
prolongation of cardiac repolarization in phase
II studies; the studies were subsequently
stopped.
Thalidomide
 The R-enantiomer is an effective sedative,
which has a soothing effect that relieves
anxiety and makes the patient drowsy;
 S-enantiomer is known to cause teratogenic
birth defects.
Polarimetry
 Non-destructive method of determing the
optical activity of substances.
 Measures the rotation of the polarized light as it
passes through an optically active compound.
 This method is mainly used in the determination
of the unknown solution concentrations.
 A substance is said to be optically active if it
rotates the plane of the polarized light.
Optical activity phenomenon
 When the polarized light passes through the
optically active substance and rotates the
plane of polarized light to the left side, or
clockwise, then the compound is known as the
dextrorotatory substance. If the rotation is
observed in the right side, or anti-clockwise
direction, then the compound is known as the
levorotatory substance.
 The rotation of the plane polarized light is
mainly based upon the asymmetric molecules
and the steric configuration. The rotation is
directly proportional to the concentration and
the path length. The angle of rotation is
calculated by Biot's formula:

α = [α]D25 × C × d
 α = [α]D25 × C × d

 C = concentration of the sample solution

 d = path length of the sample cell
 [α]D25 = specific rotation of the sample at D line
of the sodium at 25°C
 Factors affecting the optical activity:
◦ Nature of the sample
◦ Concentration
◦ Length of the sample tube
◦ Wavelength of the incident light
◦ Temperature of the sample solution
Instrumentation
 Source
 Filter
 Sample cell
 Analyzer
 Detector
Instrumentation
 Source
◦ Generally, sodium vapour lamp is employed. This
produces wavelengths above 450 nm.
Instrumentation
 Source
 Filter
 Sample cell
 Analyzer
 Detector
Instrumentation
 Filter
◦ Filter is mainly used to polychromatic light into
monochromatic light by absorbing the undesired
radiation.
Instrumentation
 Sample cell
◦ Sample cells are long tubes which are made up of
glass.
Instrumentation
 Analyzer
◦ A nicol prism is used for this purpose. This is mainly
used to analyze the samples whether they rotate the
plane of polarized light on the right or left side.
Instrumentation
 Detector
◦ The photomultiplier tube is commonly employed for
the detection of the wavelength.
Applications
 Used in the determination of the unknown
solutions concentration
 Used in the identification of several compounds
 Used in quantitative determinations in the sugar
industry
 Used in proteomics
 Used in the determination of the optical purity
of substances
 Used in the determination of chiral compounds
Advantages
 Simple
 Random analysis
 Simple sample preparation
Disadvantages
 Only optically active substances can be
measured
 Less accurate
 Less reproducibility
 High interferences