Excitation, electronic pigments

This pair of chlorophyll molecules, which as we shall see accepts photons and thereby excites electrons, is close to the membrane surface on the periplasmic side. At the other side of the membrane the symmetry axis passes through the Fe atom. The remaining pigments are symmetrically arranged on each side of the symmetry axis (Figure 12.15). Two bacteriochlorophyll molecules, the accessory chlorophylls, make hydrophobic contacts with the special pair of chlorophylls on one side and with the pheophytin molecules on the other side. Both the accessory chlorophyll molecules and the pheophytin molecules are bound between transmembrane helices from both subunits in pockets lined by hydrophobic residues from the transmembrane helices (Figure 12.16). 

Figure 5-1. Schematic representation of the three stages of photosynthesis in chloroplasts (1) The absorption of light can excite photosynthetic pigments, leading to the photochemical events in which electrons are donated by special chlorophylls. (2) The elections are then transferred along a series of molecules, causing the oxidized form of nicotinamide adenine dinucleotide phosphate (NADP+) to become the reduced form (NADPH) ATP formation is coupled to the electron transfer steps. (3) The biochemistry of photosynthesis can proceed in the dark and requires 3 mol of ATP and 2 mol of NADPH per mole of C02 fixed into a carbohydrate, represented in the figure by (CH20).

Green plants possess two distinct pigment systems (PS I and PS II), which provide for a noncyclic flow of electrons (Fig. 3-6). Light absorption by PS I excites electrons to an energy level capable of reducing ferredoxin via a... 

Absorption of light by a molecule excites it from the ground state to a higher electronic state. With photosynthetic pigments, the excited electron occupies a IT orbital in the system of conjugated double bonds of the porphyrin. The excitation energy in photosynthesis is harvested in two ways ... 

Photophosphorylation Phosphorylation of ADP to ATP that depends directly on energy from sunlight. The light energy is captured by a pigment such as chlorophyll and is passed in the form of excited electrons to an electron transport chain the electron transport chain uses energy from... 

Beta-cartone sits in the aphid s cell membranes like the red molecule in the pink-lake bacteria. It collects light, which (through an unknown mechanism) excites electrons and pushes them onto an NADH-Uke electron box. Then the electrons are used to make ATP. Overall, sunlight hits the carrot pigment, and its energy is turned into ATP for the aphid to live on. Could this aphid be made an honorary plant ... 

Photosystem I. contains chlorophyll a and other pigments that "trap" photons, exciting electrons. The excited electrons leave the system and reduce ferredoxin. The system is returned to the ground state by electrons from the electron transport chain. 

So far we have exclusively discussed time-resolved absorption spectroscopy with visible femtosecond pulses. It has become recently feasible to perfomi time-resolved spectroscopy with femtosecond IR pulses. Flochstrasser and co-workers [M, 150. 151. 152. 153. 154. 155. 156 and 157] have worked out methods to employ IR pulses to monitor chemical reactions following electronic excitation by visible pump pulses these methods were applied in work on the light-initiated charge-transfer reactions that occur in the photosynthetic reaction centre [156. 157] and on the excited-state isomerization of tlie retinal pigment in bacteriorhodopsin [155]. Walker and co-workers [158] have recently used femtosecond IR spectroscopy to study vibrational dynamics associated with intramolecular charge transfer these studies are complementary to those perfomied by Barbara and co-workers [159. 160], in which ground-state RISRS wavepackets were monitored using a dynamic-absorption technique with visible pulses. 

Resonance Raman Spectroscopy. If the excitation wavelength is chosen to correspond to an absorption maximum of the species being studied, a 10 —10 enhancement of the Raman scatter of the chromophore is observed. This effect is called resonance enhancement or resonance Raman (RR) spectroscopy. There are several mechanisms to explain this phenomenon, the most common of which is Franck-Condon enhancement. In this case, a band intensity is enhanced if some component of the vibrational motion is along one of the directions in which the molecule expands in the electronic excited state. The intensity is roughly proportional to the distortion of the molecule along this axis. RR spectroscopy has been an important biochemical tool, and it may have industrial uses in some areas of pigment chemistry. Two biological appHcations include the deterrnination of helix transitions of deoxyribonucleic acid (DNA) (18), and the elucidation of several peptide stmctures (19). A review of topics in this area has been pubHshed (20). 

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