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For other water-soluble receptors based on cationic (N-alkyl)pyridyl porphyrins see: a) M. Sirish, V. A. Chertkov, H.-J. Schneider, Chem. Eur. J. 2002, 5, 1181-1188; b) H.-J. Schneider, L. Tianjun, M. Sirish, V. Malinovski, Tetrahedron 2002, 58, 779-786; c) M. Sirish, H.-J. Schneider, J. Am. Chem. Soc. 2000, 122, 5881-5882.
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0037147978
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For other water-soluble receptors based on cationic (N-alkyl)pyridyl porphyrins see: a) M. Sirish, V. A. Chertkov, H.-J. Schneider, Chem. Eur. J. 2002, 5, 1181-1188; b) H.-J. Schneider, L. Tianjun, M. Sirish, V. Malinovski, Tetrahedron 2002, 58, 779-786; c) M. Sirish, H.-J. Schneider, J. Am. Chem. Soc. 2000, 122, 5881-5882.
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For other water-soluble receptors based on cationic (N-alkyl)pyridyl porphyrins see: a) M. Sirish, V. A. Chertkov, H.-J. Schneider, Chem. Eur. J. 2002, 5, 1181-1188; b) H.-J. Schneider, L. Tianjun, M. Sirish, V. Malinovski, Tetrahedron 2002, 58, 779-786; c) M. Sirish, H.-J. Schneider, J. Am. Chem. Soc. 2000, 122, 5881-5882.
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0001688882
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A statistical mixture of atropoisomers is expected to be present in solution. In this case the αααβ isomer, the most abundant one, together with the αααα isomer should account for 62.5% of the mixture. NMR measurements did not provide any indications about isomer distribution. Changes seem to occur induced by complexation but are also difficult to be quantified, see T. Mizutani, T. Horiguchi, H. Koyama, I. Uratani, H. Ogoshi, Bull. Chem. Soc. Jpn. 1998, 71, 413-418.
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24
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0035065777
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A basic buffer was chosen to allow comparison of the data obtained for caffeine with that obtained for more basic guests (Tables 4 and 5) without having to consider protonation equilibria (see, M. V. Rekharsky, A. Nakamura, G. A. Hembury, Y. Inoue, Bull. Chem. Soc. Jpn. 2001, 74, 449-457). Furthermore, as shown for receptor Zn-1f in Table 1, there is not any appreciable effect on caffeine binding if the acidic oxalate buffer is used (with the exception of Zn-1c due to the ionization equilibrium involving the Tyr OH group).
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84986379497
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0242412943
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note
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-3M). Aggregation was also not observed in these conditions as proven directly by a microcalorimetric experiment on porphyrin Zn-1e (see experimental section).
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0242412944
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See reference [14a], and references therein
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See reference [14a], and references therein.
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31
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0242496219
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note
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a obtained from measurements in different concentration ranges (UV and ITC) were in good agreement.
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33
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0242412942
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note
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For an example in which the occurrence of 2:1 complexes is considered see reference [36].
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0242580659
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note
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The signals have a complex multiplicity pattern, which agrees with the presence in solution of different conformational isomers interconverting slowly on the NMR chemical shift timescale at room temperature.
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0242412940
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note
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This is not surprising since ITC measurements performed at concentrations 500-1000 times higher than UV measurements present a higher contribution coming from the existence of 2:1 species.
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45
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37049111701
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Stacking interactions between the Tyr phenol moiety and tetracationic 5,10,15,20-tetrakis-(N-methylpyridinium-4-yl)porphyrinato zinc(II) chloride salt give stabilization to the porphyrin-Tyr complex in aqueous solutions, see: a) E. Mikros, A. Gaudamer, R. Pasternack, Inorg. Chim. Acta 1988, 153, 199-200; b) C. Verchére-Bèaur, E. Mikros, M. Perrée-Fauvet, A. Gaudamer, J. Inorg. Biochem. 1990, 40, 127-139.
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Stacking interactions between the Tyr phenol moiety and tetracationic 5,10,15,20-tetrakis-(N-methylpyridinium-4-yl)porphyrinato zinc(II) chloride salt give stabilization to the porphyrin-Tyr complex in aqueous solutions, see: a) E. Mikros, A. Gaudamer, R. Pasternack, Inorg. Chim. Acta 1988, 153, 199-200; b) C. Verchére-Bèaur, E. Mikros, M. Perrée-Fauvet, A. Gaudamer, J. Inorg. Biochem. 1990, 40, 127-139.
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0242664634
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The difference observed between Zn-1c and metal-free 1c is δ = 0.1.
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53
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4244064293
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54
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0242664633
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note
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From electronic considerations, imidazole and 1-methylimidazole should be better ligands than caffeine, as they more basic.
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56
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