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Kendric C. Smith
Emeritus Professor, Radiation Oncology (Radiation Biology)
Stanford University School of Medicine
800 Blossom Hill Road, Unit R169, Los Gatos, CA 95032
kendric@stanford.edu
web.stanford.edu/~kendric/
Photochemistry is the underlying mechanism for all of photobiology.
When a molecule absorbs a photon of light, its electronic structure
changes, and it reacts differently with other molecules. The energy
that is absorbed from light can result in photochemical changes in
the absorbing molecule, or in an adjacent molecule (e.g.,
photosensitization). The energy can also be given off as heat, or as
lower energy light, i.e., fluorescence or phosphorescence, in order
to return the molecule to its ground state. Each type of molecule
has a different preference for which of these different mechanisms it
uses to get rid of absorbed photon energy, e.g., some prefer
fluorescence over chemistry.
The Basic Laws of Photochemistry
The First Law of Photochemistry states that light must be
absorbed for photochemistry to occur. This is a simple concept, but
it is the basis for performing photochemical and photobiological
experiments correctly. If light of a particular wavelength is not
absorbed by a system, no photochemistry will occur, and no
photobiological effects will be observed, no matter how long one
irradiates with that wavelength of light.
Figure 1. An electromagnetic wave showing the perpendicularlyoriented waves of electric and magnetic fields, and the characteristic
wavelength () of the radiation.
The electromagnetic spectrum is composed of different wavelengths
of light having different photon energies, and is classified into the
regions shown in Figure 2. Note that the regions of interest for
photochemistry, i.e., visible and ultraviolet (UV), are only a small
part of the full electromagnetic spectrum. Longer wavelengths, e.g.,
far infrared, tend to cause the vibrational excitation of molecules,
which results in heating. Shorter wavelength X-rays cause
ionization.
From this relationship, one can determine the quantum yield for
each process. It is simply the rate of that process as a fraction of all
pathways for the loss of energy.
Intermolecular Processes: Excited State Quenching
When a second molecule (a quencher, Q) interacts with a molecule
in an excited state, new ways may be created for the excited state
species to lose its energy of excitation. Such interactions (collisions)
can induce the loss of energy in the form of heat, which is called
physical quenching, or it can cause the energy to be transferred to
the second molecule with or without the transfer of an electron. The
former is called energy transfer, and the latter, electron transfer.
Formally, one can write:
Where
is the intensity, or rate of fluorescence, without a
quencher; is the intensity, or rate of fluorescence, with a
quencher;
is the quencher rate coefficient; is the fluorescence
lifetime of A without a quencher present, and
is the
concentration of the quencher. This relationship is referred to as
the Stern-Volmer equation.
Types of Photochemical Reactions
1. Linear addition to an unsaturated molecule, e.g., the pyrimidine
base, thymne, in DNA can combine with the amino acid residue,
cysteine, in proteins. This is a model for the photochemical
crosslinking of DNA and proteins by UV radiation (see the Module
on DNA-Protein Crosslinks).
Suggested Reading
Coxon, JM and Halton, B, Organic Photochemistry, Cambridge
University Press, 1987
Gilbert, A and Baggott, J, Essentials of Molecular Photochemistry,
Blackwell Science Ltd, 1990.
Kagan, J, Organic Photochemistry: Principles and Applications,
Academic Press, 1993.
Klessinger, M and Michl, J, Excited States and Photo-Chemistry of
Organic Molecules, Wiley-VCH, 1995.
Smith, K.C., The Science of Photobiology, 2nd Ed. Plenum Pub Corp,
1989.
Turro, NT, Modern Molecular Photochemistry, University Science
Books, 1991.
Wayne, CE and Wayne, RP, Photochemistry, Oxford University
Press, 1996.