Micelles and Hollow Nanospheres Based on e - Caprolactone - Containing Polymers in Aqueous Media
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2950 1 2002 WILEY-VCH Verlag GmbH&Co. KGaA, Weinheim 0044-8249/02/4116-2950 $ 20.00+.50/0 Angew. Chem. Int. Ed. 2002, 41, No. 16 n) V. Krμl, O. Rusin, J. Charvμtovμ, P. Anzenbacher, Jr., J. Fogl, Tetrahedron Lett. 2000, 41, 10147 ± 10151; o) N. Sugimoto, D. Miyoshi, J. Zou, Chem. Commun. 2000, 2295 ± 2296. [6] Studies in polar or apolar organic media: a) R. P. Bonar-Law, A. P. Davis, B. A. Murray, Angew. Chem. 1990, 102, 1497 ± 1499; Angew. Chem. Int. Ed. Engl. 1990, 30, 1407 ± 1409; b) A. P. Davis, R. S. Wareham, Angew. Chem. 1998, 110, 2397 ± 2400; Angew. Chem. Int. Ed. 1998, 37, 2270 ± 2273; c) R. Liu, W. C. Still, Tetrahedron Lett. 1993, 34, 2573 ± 2576; d) P. B. Savage, S. H. Gellman, J. Am. Chem. Soc. 1993, 115, 10448 ± 10449; e) C.-Y. Huang, L. A. Cabell, E. V. Anslyn, J. Am. Chem. Soc. 1994, 116, 2778 ± 2792; f) R. P. Bonar-Law, J. K. M. Sanders, J. Am. Chem. Soc. 1995, 117, 259 ± 271; g) J. Cuntze, L. Owens, V. Alcazar, P. Seiler, F. Diederich, Helv. Chim. Acta 1995, 78, 367 ± 390; h) S. Anderson, U. Neidlein, V. Gramlich, F. Diedrich, Angew. Chem. 1995, 107, 1722 ± 1725; Angew. Chem. Int. Ed. Engl. 1995, 34, 1596 ± 1599; i) U. Neidlein, F. Diederich, Chem. Commun. 1996, 1493 ± 1494; j) A. B‰hr, A. S. Droz, M. P ̧ntener, U. Neidlein, S. Anderson, P. Seiler, F. Diederich, Helv. Chim. Acta 1998, 81, 1931 ± 1963; k) D. K. Smith, A. Zingg, F. Diederich, Helv. Chim. Acta 1999, 82, 1225 ± 1241; l) A. B‰hr, B. Felber, K. Schneider, F. Diederich,Helv. Chim. Acta 2000, 83, 1346 ± 1376; m) T. Mizutani, T. Murakami, N. Matsumi, T. Kurahashi, H. Ogoshi, J. Chem. Soc. Chem. Commun. 1995, 1257 ± 1258; n) G. Das, A. D. Hamilton, Tetrahedron Lett. 1997, 38, 3675 ± 3678; o) M. Inouye, T. Miyake, M. Furusyo, H. Nakazumi, J. Am. Chem. Soc. 1995, 117, 12416 ± 12425; p) M. Inouye, K. Takahashi, H. Nakazumi, J. Am. Chem. Soc. 1999, 121, 341 ± 345; q) M. Inouye, K. J. Chiba, H. Nakazumi, J. Org. Chem. 1999, 64, 8170 ± 8178; r) J. M. CoterÛn, F. Hacket, H.-J. Schneider, J. Org. Chem. 1996, 61, 1429 ± 1435; s) M. Mazik, H. Bandmann, W. Sicking, Angew. Chem. 2000, 112, 562 ± 565; Angew. Chem. Int. Ed. 2000, 39, 551 ± 554; t) M. Mazik, W. Sicking,Chem. Eur. J. 2001, 7, 664 ± 670; u) H.-J. Kim, Y.-H. Kim, J.I. Hong, Tetrahedron Lett. 2001, 42, 5049 ± 5052. [7] Similar tetraureas were previously synthesized and used as anion receptors by Burns and co-workers; R. C. Jagessar, M. Shang, W. R. Scheidt, D. H. Burns, J. Am. Chem. Soc. 1998, 120, 11684 ± 11692. [8] a) J. P. Collman, R. R. Gagne, C. A. Reed, T. R. Halbert, G. Long, W. T. Robinson, J. Am. Chem. Soc. 1975, 97, 1424 ± 1439; b) J. S. Lindsey, J. Org. Chem. 1980, 45, 5215. [9] a) 1a : 1H NMR (300 MHz, [D6]DMSO): d1⁄4 2.66 (s, 2H; imideNH), 2.57 (d, J1⁄4 4.1 Hz, 8H; CHCH2CO2CH3), 3.25, (s, 12H; CHCH2CO2CH3), 4.49 (m, 4H; PhCH2O2CCHCH2CO2CH3), 4.97 (s, 8H; PhCH2O2CCHCH2CO2CH3), 6.82 (br, 4H; urea-NH), 7.23±7.35 (m, 24H; benzyl-ArH andmeso-phenyl-ArH), 7.48 (d, J1⁄4 7.7 Hz, 4H; meso-phenyl-ArH), 7.73 (t, 4H, J1⁄4 8.1 Hz;meso-phenyl-ArH), 7.90 (s, 4H; urea-NH), 8.47 (d, J1⁄4 8.1 Hz, 4H; meso-phenyl-ArH), 8.66 ppm (br, 8H; b-pyrrolic-CH); 13C NMR (100.6 MHz, [D6]DMSO): d1⁄4 36.84, 49.82, 52.16, 66.98, 116.76, 121.97, 128.53, 128.87, 129.18, 129.91, 131.59, 132.40, 136.49, 140.05, 155.95, 171.50, 171.95 ppm; MALDI-TOF MS: m/z : 1727.8 [MHþ];b) 1b : 1H NMR (300 MHz, [D6]DMSO): d1⁄4 2.5 (br, 8H; CHCH2CO2CH3), 3.24, (s, 12H; CHCH2CO2CH3), 4.41 (m, 4H; PhCH2O2CCHCH2CO2CH3), 4.95 (s, 8H; PhCH2O2CCHCH2CO2CH3), 6.78 (br, 4H; urea-NH), 7.22±7.32 (m, 24H; benzyl-ArH and meso-phenyl-ArH), 7.49 (s, 4H; urea-NH), 7.58 (d, J1⁄4 6.3 Hz, 4H; meso-phenyl-ArH), 7.71 (t, 4H, J1⁄4 8.0 Hz; meso-phenyl-ArH ), 8.39 (d, J1⁄4 8.4 Hz, 4H; meso-phenyl-ArH), 8.61 ppm (dd, J1⁄4 11.6, 4.5 Hz, 8H; b-pyrrolic-CH); 13C NMR (75 MHz, CDCl3): d1⁄4 36.72, 49.60, 52.17, 67.68, 116.01, 123.23, 123.61, 128.48, 128.78, 128.90, 129.82, 131.96, 132.11, 134.96, 135.41, 139.74, 150.55, 150.64, 155.72, 171.76 ppm; MALDI-TOF MS: m/z : 1790.7 [MHþ]. [10] MacroModel 7.0 with modified MM2 force field. F. Mohamadi, N. G. J. Richards, W. C. Guida, R. Liskamp, M. Lipton, C. Caufield, G. Chang, T. Hendrickson, W. C. Still, J. Comput. Chem. 1990, 11, 440. [11] Compound 1b does not exist in dimeric or oligomeric forms below 1 mm concentration; this was inferred from the 1H NMR dilution titration of urea-appended porphyrins in CDCl3. In addition, chiral urea-appended porphyrin analogues without carbonyl groups did not exhibit distinct biphasic CD in the Soret region. Therefore, the distinct CD signs do not originate from the exciton coupling between porphyrins. While approximately symmetrical, the shape of the CD spectrum of 1b is similar to that obtained from the coupling of two porphyrins, and is also similar to induced CD spectra from the Micelles and Hollow Nanospheres Based on eCaprolactone-Containing Polymers in Aqueous Media**
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