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DOI 10.1007/s11120-009-9434-2
REVIEW
Received: 8 January 2009 / Accepted: 6 May 2009 / Published online: 19 June 2009
Springer Science+Business Media B.V. 2009
G. Renger (&)
Institut fur Chemie, Max-Volmer-Laboratorium fur
Biophysikalische Chemie, Technische Universitat Berlin,
Strae des 17. Juni 135, 10623 Berlin, Germany
e-mail: rengsbbc@mailbox.tu-berlin.de;
Gernot.Renger@alumni.TU-Berlin.DE
B. Hanssum
Wissenschaftliche Geratebau Dr. Ing. Herbert Knauer GmbH,
Hegauer Weg 38, 14163 Berlin, Germany
Introduction
The dioxygen molecule O2 plays a paramount role for the
existence of all higher forms of life on earth. It provides the
unique and indispensable oxidant for highly efficient Gibbs
energy extraction from food via aerobic respiration. The
cold combustion of these substances with O2 enhances
the specific amount of available Gibbs energy by more than
a factor of 10 compared to their corresponding catabolism
under anaerobic conditions (for discussion, see Nicholls
and Ferguson 1982; Renger 1983). Most interestingly,
virtually all molecular oxygen of the atmosphere and that
dissolved in oceans and lakes originates from a single
source, i.e., the light-driven water splitting of oxygenic
photosynthesis (Kasting and Seifert 2002). The invention
of a system that enables the light driven splitting of water
into molecular oxygen and metabolically bound hydrogen
occurred 23 billion years ago at the evolutionary level of
prokaryotic cyanobacteria (Buick 1992; de Marais 2000;
Xiong and Bauer 2002; Larkum 2008). This event led to
the present day aerobic atmosphere (Kasting and Seifert
2002; Lane 2003) and the generation of the stratospheric
ozone layer as the indispensable protective umbrella
against deleterious UV-B irradiation (for a review, see
Worrest and Coldwell 1986).
Molecular dioxygen is characterized by unique properties. Of paramount importance for the biosphere is the triplet
spin multiplicity of its electronic ground state which is
P
characterized by the term symbol 3 g O2 . In this configuration the O2 molecule can only form a spin forbidden
123
488
123
489
DE
RT
PO2 1
ln
4F
PO2 2
Luminescence quenching
Molecular oxygen is a strong quencher of electronically
excited states of pigments. This effect gives rise to changes
of the luminescence emission from these probes. The
quantum yield and in case of dynamic quenching also the
kinetics of the emission depend on the concentration of the
quencher (Stern Volmer equation, for details, see Lakowicz
1999) and therefore quantum yield or lifetime measurements can be used for monitoring the dioxygen content.
Several approaches have been developed in particular for
medical applications in analyses of cell tissues (Lippitsch
et al. 1988; Klimant et al. 1999; Chodavarapu et al. 2007).
However, this methodology is not often used for studies of
photosynthetically evolved oxygen.
Biological sensoring
The oldest qualitative method that actually contributed to
the discovery of molecular dioxygen by J. Priestley was the
classical experiment with a mouse kept in a closed box
either without or together with a mint plant. In this case the
cytochrome c oxidase (COX) of the respiratory chain in the
mitochondria of the mouse was the biosensor for oxygen
(Priestley 1772). The basic underlying principle of the
biosensor assay originally used by Priestley has been
applied by Lavergne two centuries later for monitoring the
123
490
Mass spectrometry
123
3a
3b
Ag-anode : 4Ag 4Cl ! 4AgCl 4e
In order to obtain a linear response to the O2 concentration the system operates in the range of the diffusion
limited electric current ID. A polarization voltage of the
cathode of about -0.7 V is usually applied. Under these
conditions the ID is given by the relation (see Atkins 2001).
ID z F C D
A
d
where z = number of electrons participating in the reaction, F = Faraday constant (9.6485 9 104 C/mol),
491
O2 H2 O 1 V m
3600
Sc V c
Chl
4a
123
492
123
493
123
494
Zt
I tdt
123
6
state transition matrix T are
1
0 b 2 c3
a 1 0 b3 C
C
7
c 1 a2 0 A
b1 c 2 a 3
Y n 1 a3 S3 n1 b2 S2 n1
495
123
496
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