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This limiting ratio can be predicted for any gradient-pH combination, provided the pKa values of the molecule, the unstirred water layer (UWL) Pu, and the intrinsic P0 permeabilities were known [25] (The topic of the UWL are discussed in greater detail in Section 776) In gradient pH assays, it is sometimes observed that nearly all the samples move to the acceptor side, due to the sink conditions created, sometimes limiting the determination of concentrations Shorter permeation times solve the problem, a welcome prospect in a high-throughput application A 3 4-h period suf ces, which is a considerable reduction over the original 15 h permeation time [547,550] Shorter times would lead to greater uncertainties in the calculated permeability, since the approximate lag time tLAG can be as long as one hour for the most lipophilic molecules 7532 Double Sink: Eq (734) in the Presence of Serum Protein or Sink in Acceptor Wells If serum protein or surfactant is added to the acceptor wells, then, in general, A!D D!A Pe and Pe are not the same, even under iso-pH conditions The acceptorto-donor permeability needs to be solved by performing a separate iso-pH assay, where the serum protein or surfactant is added to the donor side, instead of the acceptor side The value of Pe is determined, using Eq (720), and used in A!D gradient-pH cases in place of Pe , as described in the preceding section The gradient-pH calculation procedure is iterative as well Figure 717 shows the asymmetry ratios of a series of compounds (acids, bases, and neutrals) determined at iso-pH 74, under the in uence of sink conditions created not by pH, but by anionic surfactant added to the acceptor wells (discuss later in the chapter) The membrane barrier was constructed from 20% soy lecithin in dodecane All molecules show an upward dependence on lipophilicity, as estimated by octanol water apparent partition coef cients, log Kd(74) The bases are extensively cationic at pH 74, as well as being lipophilic, and so display the highest responses to the sink condition They are driven to interact with the surfactant by both hydrophobic and electrostatic forces The anionic acids are largely indifferent.

log ra = log [ (VD/ VA) Pe(A->D) / Pe(D->A) ]

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massive ads, 54 of them full-page To generate sales for the 1933 Christmas season, the company took out a four-page, four-color ad in the Chicago Tribune26 When Americans started listening to the radio, Walgreens saturated that medium, too In 1931, Walgreens became the first drugstore chain in the country to advertise on the talk box, sponsoring popular shows from Ben Potter, Boy Detective (who was no relation to Harry) to Hit Tunes of the Week (a predecessor to Kasey Kasem s American Top 40), featuring such stars as Tommy Dorsey, Guy Lombardo, and Benny Goodman27 Walgreens wisely recruited Bob Elson, the voice of the Chicago Cubs, to become the voice of Walgreens, too (His brother Charles enjoyed a long Walgreens career) Elson s trademark delivery was smooth and monotone perfect for the low-profile Walgreens corporation and he used it well enough to earn his spot in the broadcasters wing of the Baseball Hall of Fame But it has to be said that Walgreens wasn t Elson s only favorite store Hall of Fame pitcher Jim Kaat, who grew up in southwestern Michigan listening to Elson s broadcasts, recalls the legendary announcer telling him, Kid, when you re paid as lousy as we are, you gotta try the market Elson persuaded Kaat to invest in Magnavox, which earned both a small fortune28 Elson, later nicknamed the Old Commander because he served in the US Navy during World War II, also padded his income by plugging just about any company, car wash, or corner barbershop that asked him often during games, without the Cubs knowledge of his financial arrangement As fellow Hall of Fame broadcaster Lindsey Nelson recalled, I ve never heard anybody do as much shilling when he was on the air We used to kid that Elson had to be on the take Bob d mosey along and say, There s ball two and speaking of ball, did we have one last night at Rosa Mesa s Restaurant! The [Cubs] never got a penny for Bob s shilling Say what you will about the Old Commander If shilling was an art, Bob raised it to a new plateau 29 Perhaps Walgreens was lucky to catch Elson early in his career, when.