Distribution of iodide between cells and plasma as measured by means of radioactive iodide.
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Second-order rate constants have been determined for the title reactions in OH(-)/H(2)O and in OH(-)/ (CH(3)CN/H(2)O) [30/70, 60/40, and 85/15 (v/v) mixtures]. A relatively small increase in reactivity is observed for the four substrates upon increasing the percentage of CH(3)CN in the solvent mixture. The methyl activating factors (/) are also slightly affected by the solvent composition. On the other hand, the high acceleration of the reaction by methylation of the pyridine ring amounts to 10(4)-10(6) according to an E1cb mechanism.
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Both of the title compounds, catena-poly[[[tetraaquamagnesium(I)]-micro-4,4'-bipyridine-kappa(2)N:N'] diiodide bis(4,4'-bipyridine) solvate], [[Mg(C(10)H(8)N(2))(H(2)O)(4)]I(2).2C(10)H(8)N(2)](n), (I), and catena-poly[[[micro-4,4'-bipyridine-bis[diiodobis(propan-1-ol)strontium(I)]]-di-micro-4,4'-bipyridine-kappa(4)N:N'] bis(4,4'-bipyridine) solvate], [[Sr(2)I(4)(C(10)H(8)N(2))(3)(C(3)H(8)O)(4)].2C(10)H(8)N(2)](n), (II), are one-dimensional polymers which are single- and double-stranded, respectively, the metal atoms being linked by the 4,4'-bipyridine moieties. The Mg complex, (I), is [cis-[(H(2)O)(4)Mg(N-4,4'-bipyridine-N')((2/2))]](( infinity | infinity ))I(2).4,4'-bipyridine and Mg has a six-coordinate quasi-octahedral coordination environment. The Sr complex, (II), is isomorphous with its previously defined Ba counterpart [Kepert, Waters & White (1996). Aust. J. Chem. 49, 117-135], being [(propan-1-ol)(2)I(2)Sr(N-4,4'-bipyridine-N')((3/2))](( infinity | infinity )).4,4'-bipyridine, with the I atoms trans-axial in a seven-coordinate pentagonal-bipyramidal Sr environment.
The title compound crystallizes in the orthorhombic, noncentrosymmetric space group Pna2(1) with a = 10.241(11), b = 12.903(12), c = 9.312(9) A and with one formula unit per asymmetric unit. The stereochemically comparable torsion angles of the cation of 1 and of acetylcholine chloride are analogous. In the crystal structure the trimethylammonio methyl group is surrounded by three anions in the first coordination sphere. The geometry of a triangle formed by one of these counterions which occupies a special face of the N+C4 tetrahedron of the (CH3)3N+-CH2-R moiety, the nitrogen atom of the ammonium group and the oxygen atom of the carbonyl group is typical for nicotinic agonists.
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1. The iodide space in rabbit brain varies greatly depending on the conditions under which it is determined.2. When (131)I(-) only is used the iodide space 4 hr after administration of the marker is of the order of 2%. The iodide content of the cerebrospinal fluid (c.s.f.) is about 1% of that of the serum.3. Depression of the active iodide transport by perchlorate increases the space to 8.2% and the iodide content of the c.s.f. to 26% of that of the serum.4. The active iodide transport can also be depressed by saturation with unlabelled iodide. Up to a serum iodide concentration of 5 mM the space determined after 5 hr remained constant at 2.7%. The iodide space grew when the serum iodide content was enhanced from 5 to 20 mM, to become constant at a value of 10.6% on further increase of the serum iodide (up to 50 mM). The iodide content of the c.s.f. increased in a similar manner as the space with the iodide concentration of the serum to about 1/3 of the serum concentration. The iodide space of the muscle was independent of the plasma iodide content.5. From 4 to 8 hr after administration of (131)I(-) alone or with unlabelled iodide (to a serum concentration of 15 mM) the iodide space remained relatively constant.6. When (131)I(-) was administered in the fluid with which the ventricles were perfused an iodide space of about 7% was attained after about 5 hr.7. In experiments in which (131)I(-) was administered intravenously and the sink action of the c.s.f. was eliminated by perfusion of the ventricles with a perfusate containing as much (131)I(-) as the plasma, the iodide space was 10.2%. When in addition active iodide transport was depressed by perchlorate the space increased to 16.8%.8. Intravenous administration of labelled and unlabelled iodide (to a serum concentration of 20-40 mM) and ventricle perfusion with the same concentration of (131)I(-) and unlabelled iodide as in the plasma yielded an iodide space of 20.8%. In similar experiments the iodide concentration of the perfusate was so adjusted that after 5 hr perfusion its iodide content hardly changed during the passage through the ventricles. Under these conditions the iodide concentration of the extracellular and perfusion fluids can be considered to be near equal. The iodide space computed on the basis of the iodide content of the outflowing fluid was 22.5%.9. The large iodide space could be equated with the extracellular space if the iodide remained extracellular. This seems to be the case in the muscle where the iodide space is similar to the inulin space.10. The large effects on the iodide space of perchlorate and saturation with unlabelled iodide in experiments in which the marker was administered intravenously and in the perfusate (7 and 8) suggests the presence of an active iodide transport from the brain extracellular fluid into the blood over the blood-brain barrier.