Hole, positively charged

In an extrinsic semiconductor, tlie conductivity is dominated by tlie e (or h ) in tlie CB (or VB) provided by shallow donors (or acceptors). If tlie dominant charge carriers are negative (electrons), tlie material is called n type. If tlie conduction is dominated by holes (positive charge carriers), tlie material is called p type. 

Figure 1-1. Schematic drawing of a single-layer electroluminescent device. An applied electric field leads to injection of holes (positive charges the majortiy charge carriers in polymers such as PPV) and electrons (usually the minority charge carriers) into the light-emitting polymer film from the two electrode contacts. Formation of an electron-hole pair within the polymer may then result in the emission of a photon. Since holes migrate much more easily through PPV than electrons, electron-hole recombination takes place in the vicinity of the cathode.

In a defect-free, undoped, semiconductor, tliere are no energy states witliin tire gap. At 7"= 0 K, all of tire VB states are occupied by electrons and all of the CB states are empty, resulting in zero conductivity. The tliennal excitation of electrons across tire gap becomes possible at T > 0 and a net electron concentration in tire CB is established. The electrons excited into tire CB leave empty states in tire VB. These holes behave like positively charged electrons. Botli tire electrons in the CB and holes in tire VB participate in tire electrical conductivity. 

When a sibcon crystal is doped with atoms of elements having a valence of less than four, eg, boron or gallium (valence = 3), only three of the four covalent bonds of the adjacent sibcon atoms are occupied. The vacancy at an unoccupied covalent bond constitutes a hole. Dopants that contribute holes, which in turn act like positive charge carriers, are acceptor dopants and the resulting crystal is -type (positive) sibcon (Fig. Id). 

Copper(I) oxide [1317-39-1] is 2lp-ty e semiconductor, Cu2 0, in which proper vacancies act as acceptors to create electron holes that conduct within a narrow band in the Cu i7-orbitals. Nickel monoxide [1313-99-17, NiO, forms a deficient semiconductor in which vacancies occur in cation sites similar to those for cuprous oxide. For each cation vacancy two electron holes must be formed, the latter assumed to be associated with regular cations ([Ni " h = Semiconduction results from the transfer of positive charges from cation to cation through the lattice. Conduction of this type is similar... 

Here Oq represents the oxide ion which is incorporated, IT represents the Ni + ion which is a positive hole, and an exU a negative charge being indicated by the superscript dot, thus V/,j is the vacant cation site where tire double dot represents the absence of two positive charges at that site. 

The single mutation Asp 32-Ala reduces the catalytic reaction rate by a factor of about lO compared with wild type. This rate reduction reflects the role of Asp 32 in stabilizing the positive charge that His 64 acquires in the transition state. A similar reduction of kcat and kcat/ m (2.5 x 10 ) is obtained for the single mutant Asn 155-Thr. Asn 155 provides one of the two hydrogen bonds to the substrate transition state in the oxyanion hole of subtilisin. 

Exercise 7.4. (a) Use the parameters of Table 7.3 and the LD model to calculate the activation energy of the 2— 3 step in solution, (b) Repeat the same calculation in a protein model where a positive charge of +0.5 (3 A from the carbonyl carbon) represents the oxyanion holes, while a negative charge of -0.5 near the His+ residue represents the somewhat screened Asp 102. Simulate the rest of the system by the LD model. 

Fig. 20 Vertical model of complementary assembly of peptide mixtures. Hydrophobic interactions are represented by the interlocking of raised sections and holes. The axis is indicated by dots. Reproduced from Takahashi et al. [57] with permission. Copyright Wiley-VCH. Numbers refer to the peptide entries in Fig. 18. Positively charged residues are dark shaded in contrast with the negatively charged residues which are light shaded...

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