Section 1 Electron Flow

Look closely at the acid-base reaction in Figure 2.5, and note how it is shown. Dimethyl ether, the Lewis base, donates an electron pair to a vacant valence orbital of the boron atom in BF3, a Lewis acid. The direction of electron-pair flow from the base to acid is shown using curved arrows, just as the direction of electron flow in going from one resonance structure to another was shown using curved arrows in Section 2.5. A cuived arrow always means that a pair of electrons moves from the atom at the tail of the arrow to the atom at the head of the arrow. We ll use this curved-arrow notation throughout the remainder of this text to indicate electron flow during reactions. 

We saw in Section 7.8 that bromohydrins are converted into epoxides when treated with base. Propose a mechanism, using curved arrows to show the electron flow. 

Acid-catalyzed hydrolysis of a nitrile to give a carboxylic acid occurs by initial protonation of the nitrogen atom, followed by nucleophilic addition of water. Review the mechanism of base-catalyzed nitrile hydrolysis in Section 20.7, and then write all the steps involved in the acicl-catalyzed reaction, using curved arrows to represent electron flow in each step. 

Write a balanced reaction for the spontaneous process when we allow a path for electron flow between the O2/H2O electrode and the H /H20 electrode as described in Section 5.3.3. 

The link between UpophiUcity and point charges is given by intermolecular electrostatic interactions (Sections 12.1.1.2, 12.1.3 and 12.1.4 address this topic) and ionization constants. The mathematical relationships between Upophilicity descriptors and pKjS are discussed in detail in Chapter 3 by Alex Avdeef. Here, we recall how pKj values are related to the molecular electron flow by taking the difference between the pfCj of aromatic and aUphatic amines as an example. The pfCa of a basic compound depends on the equilibrium shown in Fig. 12.2(A). A chemical effect produces the stabilization or destabiUzation of one of the two forms, the free energy difference (AG) decreases or increases and, consequently. 

The discussion above has been more or less empirical and descriptive. However, considerable effort has been made to interpret 3-SCS on a more physical basis. Electric-field effects (71-75) were invoked to explain signal shifts of 3-carbon atoms induced by protonation of amines (157,158) (cf. Section II-B-3). This approach was later extended to other functionalities by Schneider and coworkers, who assumed that the SEF component (E2) rather than inductive properties of the substituents should be responsible for 3-SCS (113). They found fairly linear correlations of 3-SCS(X ) and 3-SCS(X ) in cyclohexyl derivatives (76) and attributed the difference between these for a given X to a widening of the C -Cp-Cv bond angle by 2.2° in the axial conformer (114,159). The decrease of 3-SCS in the order primary Cp —> secondary Cp — tertiary Cp — quaternary Cp was explained by electron-charge polarization in the Cp-C" bond(s) induced by the LEF component of the C -X dipole, which is already of significance at this distance, though ( 2) still dominates (160). Such an electron flow toward the 3 carbon is expected to be much more pronounced in C-C than in C-H bonds because of the polarizability difference (aCH = 0.79 acc = 1.12) (150,151,160). 

Based on the way in which an electrode process has been illustrated, until now it would seem reasonable to assume that the only source of electron flow between the electrode and the species in solution might be attributed to faradaic processes of the type Ox + e = Red. It has already been mentioned in Section 2.3, however, that non-faradaic currents exist. Let us discuss their origin. 

Electrical and thermal conductivity are important diffusion layer properties that affect the fuel cell s overall performance. The maferial chosen to be the DL in a fuel cell must have a good electrical conductivity in order for the electron flow from the FF plates to the CLs (and vice versa) to have the least possible resistance. Similarly, the DL material must have good thermal properties so that heat generated in the active zones can be removed efficiently. Therefore, in order to choose an optimal material it is critical to be able to measure the electrical and thermal conductivity. In this section, a number of procedures used fo measure fhese paramefers will be discussed. 

Since in the steady state, it is necessary to maintain a condition of electroneutrality in any macroscopic part of the system, the total charge flux through all cross-sections of the circuit must be the same. In particular, the rate of electron flow in the external circuit is equal to the rate of charge transfer at each electrode/electrolyte interface. 

Synthesis of ATP by mitochondria is inhibited by oligomycin, which binds to the OSCP subunit of ATP synthase. On the other hand, there are processes that require energy from electron transport and that are not inhibited by oligomycin. These energy-linked processes include the transport of many ions across the mitochondrial membrane (Section E) and reverse electron flow from succinate to NAD+ (Section C,2). Dinitrophenol and many other uncouplers block the reactions, but oligomycin has no effect. This fact can be rationalized by the Mitchell hypothesis if we assume that Ap can drive these processes. 

When electrons flow from photosystem I to photosystem II, protons are transported across the chloroplast membranes as indicated in Figure E9.1. This aspect of photosynthesis will be discussed in a later section. 

Dyson speculated on the properties of a highly efficient, self-repairing, self-replicating, photosynthetic. machine for space colonization - and could not get past plants]. The photosynthetic ETC involves two ETC-linked light absorbing photosystems (photosystems I and II) and is described by the so-called Z scheme. Electron flow in downhill noncyclic and cyclic sections of the chain is coupled to ATP synthesis by noncyclic and cyclic photophosphorylation, respectively. 

Bend all in 1960 takes into consideration the results of many investigators and has become generally accepted as an overall description of electron flow in chloroplast lamellae. After introducing the concept of redox potential in Chapter 6 (Section 6.1 C), we will portray the energetics of the series representation (see Fig. 6-4, which includes many of the components that we will discuss next). 

Hie frequency of components is per 600 chlorophylls for plants growing under moderate levels of sunlight (see Table 5-1), and the order presented is in the sequence for electron flow. Redox potentials are discussed in Chapter 6 (Section 6.1C). 

For cyclic electron flow, an electron from the reduced form of ferredoxin moves back to the electron transfer chain between Photosystems I and II via the Cyt bCyclic electron flow does not involve Photosystem II, so it can be caused by far-red light absorbed only by Photosystem I — a fact that is often exploited in experimental studies. In particular, when far-red light absorbed by Photosystem I is used, cyclic electron flow can occur but noncyclic does not, so no NADPH is formed and no O2 is evolved (cyclic electron flow can lead to the formation of ATP, as is indicated in Chapter 6, Section 6.3D). When light absorbed by Photosystem II is added to cells exposed to far-red illumination, both CO2 fixation and O2 evolution can proceed, and photosynthetic enhancement is achieved. Treatment of chloroplasts or plant cells with the 02-evolution inhibitor DCMU [3-(3,4-dichlorophenyl)-l, 1-dimethyl urea], which displaces QB from its binding site for electron transfer, also leads to only cyclic electron flow DCMU therefore has many applications in the laboratory and is also an effective herbicide because it markedly inhibits photosynthesis. Cyclic electron flow may be more common in stromal lamellae because they have predominantly Photosystem I activity. 

Another class of energy storage compounds consists of redox couples such as NADP+-NADPH (Table 6-1). The reduced form, NADPH, is produced by noncyclic electron flow in chloroplasts (Chapter 5, Section 5.5C). Photosynthesis in bacteria makes use of a different redox couple, NAD+-NADH. The reduced member of this latter couple also causes an... 

In Chapter 5 (Section 5.5B), we introduced the various molecules involved with electron transfer in chloroplasts, together with a consideration of the sequence of electron flow between components (Table 5-3). Now that the concept of redox potential has been presented, we will resume our discussion of electron transfer in chloroplasts. We will compare the midpoint redox potentials of the various redox couples not only to help understand the direction of spontaneous electron flow but also to see the important role of light absorption in changing the redox properties of trap chi. Also, we will consider how ATP formation is coupled to electron flow. 

Figure 6-5 indicates that the C>2-evolution step and the electron flow mediated by the plastoquinones and the Cyt b(f complex lead to an accumulation of H+ in the lumen of a thylakoid in the light. This causes the internal H+ concentration, c, or activity, to increase. These steps depend on the light-driven electron flow, which leads to electron movement outward across the thylakoid in each of the two photosystems (see Fig. 5-19). Such movements of electrons out and protons in can increase the electrical potential inside the thylakoid (E ) relative to that outside ( °), allowing an electrical potential difference to develop across a thylakoid membrane. By the definition of chemical potential (fij = jx + RT In cij 4- ZjFE Eq. 2.4 with the pressure and gravitational terms omitted see Chapter 3, Section 3.1), the difference in chemical potential of H+ across a membrane is...

Some of the catalytic and structural properties of thioredoxin reductase as they relate to analogous properties of lipoamide dehydrogenase and glutathione reductase have been covered in Section II. The flavoprotein, thioredoxin reductase, catalyzes the electron transfer from NADPH to thioredoxin, a protein of 12,000 molecular weight containing a single disulfide. The reductase has a reactive disulfide in addition to FAD. Thus, electron flow is from NADPH to the PAD-disulfide system of thioredoxin reductase, to the disulfide of thioredoxin, and finally to a variety of acceptor systems. 

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