Photosynthesis dioxide electron transfer

The amide functionality plays an important role in the physical and chemical properties of proteins and peptides, especially in their ability to be involved in the photoinduced electron transfer process. Polyamides and proteins are known to take part in the biological electron transport mechanism for oxidation-reduction and photosynthesis processes. Therefore studies of the photochemistry of proteins or peptides are very important. Irradiation (at 254 nm) of the simplest dipeptide, glycylglycine, in aqueous solution affords carbon dioxide, ammonia and acetamide in relatively high yields and quantum yield (0.44)202 (equation 147). The reaction mechanism is thought to involve an electron transfer process. The isolation of intermediates such as IV-hydroxymethylacetamide and 7V-glycylglycyl-methyl acetamide confirmed the electron-transfer initiated free radical processes203 (equation 148). 

These are involved in a wide range of electron-transfer processes and in certain oxidation-reduction enzymes, whose function is central to such important processes as the nitrogen cycle, photosynthesis, electron transfer in mitochondria and carbon dioxide fixation. The iron-sulfur proteins display a wide range of redox potentials, from +350 mV in photosynthetic bacteria to —600 mV in chloroplasts. 

From the point of view of organic synthesis, the overall process consists of the formation of carbohydrates (CH20) by the reduction of carbon dioxide. The essence of the process is the use of photochemical energy to split water and concomitantly to reduce C02. Many proteins and small molecules are involved in photosynthetic machinery. Inorganic species are in the centre of photosynthesis as pigments in light harvesting, substrates, products, catalysts, and electron transfer mediators. 

Ferredoxins, A group of electron transfer factors found in plants and bacteria, which are non-heme iron sulfur proteins and which play an important role in photosynthesis, nitrogen and carbon dioxide fixation, and respiration. They are generally classified by the presence of either 2 or 4 iron atom clusters and an equivalent amount of inor-... 

Photosynthesis consists of two processes. The light reactions are electron transfer processes, in which water is oxidized to produce oxygen and NADP+ is reduced to produce NADPH. The dark reactions are also electron transfer processes, but here carbon dioxide is reduced to carbohydrates. 

Oxygen produced in photosynthesis comes from water. The oxygen-evolving complex is part of the series of electron-transfer reactions from water to NADPH. Carbon dioxide is involved in the dark reactions, which are different reactions that take place in another part of the chloroplast... 

In Chapter 5 we saw that, in terms of the Br0nsted-Lowry theory, acid-base reactions involve proton transfer. Another large and important group of chemical reactions, particularly in aqueous solutions, involves electron transfer these are referred to as oxidation-reduction (or redox) reactions. Redox reactions are involved (1) in photosynthesis, which releases oxygen into the Earth s atmosphere (2) in the combustion of fuels, which is responsible for rising concentrations of atmospheric carbon dioxide (3) in the formation of acid precipitation and (4) in many chemical reactions in Earth sediments. 

Another promising and fundamental aspect is the study of proton-coupled electron-transfer reactions, for example, for the study of oxygen and carbon dioxide reduction, and that of hydrogen photosynthesis. 

In plants, chlorophyll is the pigment that absorbs radiant energy from the Sun. This allows the transfer of electrons from water to carbon dioxide, creating the products glucose and oxygen. The equation for photosynthesis is ... 

The oxygen formed clearly comes from H20 and not from C02, because photosynthesis in the presence of water labeled with lgO produces oxygen labeled with 180, whereas carbon dioxide labeled with 180 does not give oxygen labeled with 180. Notice that the oxidation of the water produces two electrons, and that the formation of NADPH from NADP requires two electrons. These reactions occur at different locations within the chloroplasts and in the process of transferring electrons from the water oxidation site to the NADP reduction site, adenosine diphosphate (ADP) is converted to adenosine triphosphate (ATP see Section 15-5F for discussion of the importance of such phosphorylations). Thus electron transport between the two photoprocesses is coupled to phosphorylation. This process is called photophosphorylation (Figure 20-7). 

The essence of natural photosynthesis is the use of photochemical energy to split water and reduce CO2. Molecular oxygen is evolved in the reaction, although it appears at an earlier stage in the sequence of reactions than the reduction of carbon dioxide. Photochemical processes produce compounds of high chemical potential, which can drive a multistep synthetic sequence from CO2 to carbohydrate in a cyclic way. Reaction (16) is quite endoergic and thus thermodynamically very improbable in the dark (AG° = 522 kJ per mole of CO2 converted). Production of one molecule of oxygen and concomitant conversion of one molecule of carbon dioxide require the transfer of four electrons ... 

---