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Figure 6.1-12 The resonance Raman spectrum of [Pt(pn)2] [Pt(pn)z Br2] [Cu3Brg]2 at 80 K with A 0 = 568.2 nm excitation (Clark et al., 1980).

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of the hydrophobic effect Thomas and Seelig [397] found the partitioning of the Ca2 antagonist, unarizine (a weak base), also to be predominantly enthalpydriven, with Htr 221 kJ mol 1, again at odds with the established ideas of entropydriven partitioning of drugs The same surprise was found for the partitioning of paclitaxil [398] These observations thus appear to suggest that drugs partition into membrane phases because they are lipophilic, and not because they are hydrophobic! This needs to be investigated more extensively, using microcalorimetry

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COACHING INTO GREATNESS he s the best in his business, but he resists actively marketing and selling himself He may have some internal understanding of his greatness, but he is not Living into that Greatness Struggle is a way of hauling around old baggage Self-Expression involves examining the baggage by putting it through the X-ray machine of awareness Your job is to bring conditioned beliefs to light Once the conditioned beliefs that underlie and create struggle are identi ed, you are on your way to shifting the balance from struggle to SelfExpression And, as with all the illusions, bridging the gap between the illusion and its corresponding aptitude requires a decision

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Traffic travels through the protected LSP-Path. The link between the PLR and the MP fails. The PLR reroutes the traffic from the protected LSP-Path through the bypass tunnel as follows:

55 ELECTROSTATIC AND HYDROGEN BONDING IN A LOW-DIELECTRIC MEDIUM Section 334 pointed out that cosolvents alter aqueous ionization constants; as the dielectric constant of the mixture decreases, acids appear to have higher pKa values and bases appear (to a lesser extent than acids) to have lower values A lower dielectric constant implies that the force between charged species increases, according to Coulomb s law The equilibrium reaction in Eq (31) is shifted to the left in a decreased dielectric medium, which is the same as saying that pKa increases Numerous studies indicate that the dielectric constant in the region of the polar head groups of phospholipids is $32, the same as the value of methanol [381,446 453] Table 52 summarizes many of the results These and other values [381,406] allow us to depict the dielectric spectrum of a bilayer, shown in Fig 52 Given this view, one can think of the phospholipid bilayer as a dielectric microlamellar structure; as a solute molecule positions itself closer to the center of the hydrocarbon region, it experiences lower dielectric eld (Fig 52) At the very core, the value is near that of vacuum A diatomic molecule of Na Cl in vacuum would require more energy to separate into two distinct ions than that required to break a single carbon carbon bond! This means that ions will not easily enter the interior of bilayers without rst forming contact ion pairs It is reasonable to imagine that simple drug counterion pairs, such as (BH Cl ) will undergo exchange of charge pairs (BH for Na originally in the vicinity of PO ) on entering the head-group region, to form, PO HB), with the release of Na and Cl , as depicted in for example, ( Fig 51 We called such an imagined pairing SIP in Section 51 [149] mem An interesting hypothesis may be put forward The interfacial pKa (Fig 51) that a solute exhibits depends on the dielectric environment of its location in the bilayer Simple isotropic water-miscible solvents may be used to approximate mem pKa Pure methanol (E 32), may do well for the bilayer zone containing the phosphate groups; pure 1,4-dioxane (E 2) may mimic some of the dielectric properties of the hydrocarbon region It appears that ps Ka values of several weak bases, when mem extrapolated to 100% cosolvent, do approximate pKa values [119,162,172] ndez and Fromherz made favorable comparisons using dioxane [448] Ferna This idea is of considerable practical use, and has been largely neglected in the literature.

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