H. Liu et al. / Tetrahedron 61 (2005) 8095–8100
8099
1718, 1653, 1272, 1112 cmK1. MS (MALDI): m/z: 1257
[MCH]C, 1279 [MCNa]C. HRMS: Calcd for
C76H85N6O11: 1257.6276. Found: 1257.6268 [MCH]C.
Anal. Calcd for C76H84N6O11$H2O: C, 72.06; H, 6.78; N,
6.64. Found: C, 72.06; H, 6.47; N, 6.52.
concentration. Methanol solutions of inorganic salts were
prepared at concentrations of 0.1 M, 2.5 mL of the mixture
solution with the fixed [Zn1] or [Zn2] and the changing
concentration of guests was placed in a cuvette and the UV–
vis absorption spectrum were sequentially recorded. The
values of the absorbance at fixed wavelengths were used.
Origin6.0 software was used to fit the data to a 1:1 binding
isotherm: DAZ(DAmax/[Zn1$Zn1])!{0.5[G]C0.5([Zn1$
Zn1]CKd)K0.5[[G]2C(2[G](KdK[Zn1$Zn1])C(KdC
[Zn1$Zn1])2)1/2]}, where [G] is the salt guest concen-
4.1.6. Porphyrin H22. This compound was prepared (12%)
as purple solid from the reaction of 5b and 6 by a method
analogous to H21. Mp O230 8C. 1H NMR (CDCl3): d
K2.71 (s, 2H), 0.96 (t, JZ7.0 Hz, 6H), 1.24 (br, 8H), 1.36–
1.62 (m, 20H), 1.92 (p, JZ7.0 Hz, 4H), 2.13 (br, 8H), 2.87
(s, 8H), 4.50 (t, JZ7.1 Hz, 4H), 4.67 (s, 4H), 7.22–7.25 (m,
2H), 7.46–7.49 (m, 2H), 7.76–7.80 (m, 2H), 8.04–8.06 (m,
2H), 8.30–8.33 (m, 4H), 8.44–8.47 (m, 4H), 8.81–8.85 (m,
8H). IR (KBr): n 2925, 1718, 1653, 1271, 1115 cmK1. MS
(MALDI): m/z: 1300 [M]C. Anal. Calcd for C78H88N6O12:
C, 71.98; H, 6.81; N, 6.46. Found: 71.69; H, 6.70; N, 6.31.
tration, KdZ(Kassoc
)
K1. Association constants reported are
the average of two experiments.14
Acknowledgements
We thank the National Natural Science Foundation, the
Ministry of Science and Technology, and the State
Laboratory of Bio-organic and Natural Products Chemistry
of China for financial support.
4.1.7. Porphyrin Zn1. The free base porphyrin H21 (1.00 g,
0.08 mmol) was dissolved in dichloromethane/methanol
(3:1, 200 mL) and zinc acetate (0.60 g, 5.00 mmol) was
added with stirring. The mixture was stirred under reflux
overnight. The solvent was removed in vacuo, and the
product was subjected to column chromatography
(dichloromethane/methanol 40:1) to afford porphyrin Zn1
References and notes
1
as a purple solid in quantitative yield. Mp O260 8C. H
NMR (CDCl3): d K0.85 (t, JZ7.0 Hz, 4H), 0.32 (t, JZ
7.0 Hz, 4H), 0.98 (br, 8H), 1.36–1.90 (m, 22H), 2.89 (s, 8H),
4.23–4.67 (m, 12H), 7.20–7.25 (m, 2H), 7.40–7.43 (m, 2H),
7.71–7.72 (m, 2H), 8.00–8.09 (m, 2H), 8.31–8.33 (m, 4H),
8.46–8.49 (m, 4H), 8.80–8.85 (m, 8H). 13C NMR (CDCl3): d
14.1, 22.7, 26.1, 28.8, 29.3 (d), 31.8, 43.6, 46.8, 62.6, 65.5,
67.3 (d), 68.8, 69.4, 70.4, 71.0, 72.2, 115.2, 115.9, 117.4,
119.7, 119.8, 122.1, 127.7 (d), 129.6, 130.3, 131.6, 132.0
(d), 133.7, 134.3 (d), 134.6, 147.4, 149.4 (d), 150.0 (d),
157.1, 159.1, 166.0, 166.8 (d), 167.5. IR (KBr): n 2926,
1719, 1647, 1271, 1116 cmK1. MS (MALDI): m/z 1320
[MCH]C. Anal. Calcd for C76H82N6O11Zn: C, 69.11; H,
6.26; N, 6.36. Found: C, 69.50; H, 6.43; N, 5.98.
1. (a) Czarnik, A. W.; Yoon, J. Supramolecular Materials and
Technologies; Wiley: New York, 1999; p 177. (b) Bell, T. W.;
Hext, N. M. In Optical Biosensors; Ligler, F. S., Rowe, T.,
Chris, A., Eds.; Elsevier: Amsterdam, 2002; pp 331–368.
2. (a) Schmidtcher, F. P.; Berger, M. Chem. Rev. 1997, 97,
1609–1646. (b) Antonisse, M. M. G.; Reinhoudt, D. N. Chem.
Commun. 1998, 143–154. (c) Rebek, J., Jr. Acc. Chem. Res.
1999, 32, 278–286. (d) Snowden, T. S.; Anslyn, E. V. Chem.
Biol. 1999, 3, 740–746. (e) Gale, P. A. Coord. Chem. Rev.
2000, 199, 181–233. (f) Beer, P. D.; Gale, P. A. Angew. Chem.,
Int. Ed. 2001, 40, 486–516. (g) Sessler, J. L.; Davis, J. M. Acc.
Chem. Res. 2001, 34, 989–997. (h) Striegler, S. Curr. Org.
Chem. 2003, 7, 81–102. (i) Lee, J. W.; Samal, S.; Selvapalam,
N.; Kim, H.-J.; Kim, K. Acc. Chem. Res. 2003, 36, 621–630. (j)
Meyer, E. A.; Castellano, R. K.; Diederich, F. Angew. Chem.,
Int. Ed. 2003, 42, 1210–1250. (k) Best, M. D.; Tobey, S. L.;
Anslyn, E. V. Coord. Chem. Rev. 2003, 240, 3–15.
4.1.8. Porphyrin Zn2. This compound was prepared as a
purple solid from the reaction of H22 and zinc acetate by a
1
method similar to that for Zn1. Mp O250 8C. H NMR
(CDCl3): d 0.72 (br, 4H), 0.96 (t, JZ6.7 Hz, 8H), 1.11–1.58
(m, 18H), 1.84–1.96 (m, 8H), 2.81–2.31 (m, 8H), 4.36–4.42
(m, 4H), 4.50 (t, JZ6.5 Hz, 12H), 7.17–7.27 (m, 2H), 7.37–
7.48 (m, 2H), 7.71–7.80 (m, 2H), 7.97–8.10 (m, 2H), 8.29
(d, JZ7.8 Hz, 4H), 8.43 (d, JZ7.8 Hz, 4H), 8.75–8.91 (m,
8H). 13C NMR (CDCl3): d 14.1, 22.7, 26.2, 28.9, 29.3 (d),
31.8, 45.8 (d), 47.1 (d), 65.5, 65.7, 67.4, 67.7, 68.2, 68.9,
69.3, 69.7, 70.3, 112.9, 114.6, 116.3, 116.5, 119.4 (d),
120.9, 121.3, 127.7 (d), 129.6, 130.0, 131.7, 132.5, 133.0,
134.3, 134.8, 135.4 (d), 147.6, 149.4 (d), 150.2 (d), 157.6,
158.0, 166.9 (d), 167.1. IR (KBr): n 2924, 1718, 1653, 1271,
1114 cmK1. MS (MALDI): m/z: 1363 [MCH]C. HRMS:
Calcd for C78H86N6O12Zn: 1363.5673. Found: 1363.5689.
Anal. Calcd for C78H86N6O12Zn: C, 68.64; H, 6.35, N, 6.16.
Found: C, 68.42; H, 6.39; N, 6.11.
3. (a) Reetz, M. T. In Atwood, J. L., Davies, J. E. D., NacNicol,
¨
D. D., Vogtle, F., Lehn, J.-M., Gokel, G. W., Eds.;
Comprehensive Supramolecular Chemistry; Pergamon:
Oxford, 1996; Vol. 2, p 553. (b) Kirkovits, G. J.; Shriver, J.
A.; Gale, P. A.; Sessler, J. L. J. Inclusion Phenom. Macrocycl.
Chem. 2001, 41, 69–75. (c) Atwood, J. L.; Szumna, A. Chem.
Commun. 2003, 940–941.
4. Cyanide in Biology. Vennesland, B., Comm, E. E., Knownles,
C. J., Westly, J., Wissing, F., Eds.; Academic: London, 1981.
5. (a) Miller, G. C.; Pritsos, C. A. Cyanide: Soc. Ind. Econ.
Aspect, Proc. Symp. Annu. Meet. 2001, 73–81. (b) Richardson,
S. D. Trends Anal. Chem. 2003, 22, 666–684.
6. (a) Ikediobi, C. O.; Wen, L.; Latinwo, L. M. Am. Environ. Lab.
1997, 9, 20–21. (b) Osborn, K. E.; Okamoto, H. Water
Environ. Lab. Solutions 2003, 10, 1–5.
´ ´
7. (a) Ansenbacher, P., Jr.; Tyson, D. S.; Jursıkova, K.;
Castellano, F. N. J. Am. Chem. Soc. 2002, 124, 6232–6233.
4.2. Binding studies
´
´
(b) Ros-Lis, J. V.; Martınez-Man˜ez, R.; Soto, J. Chem.
Commun. 2002, 2248–2249. (c) Chow, C.-F.; Lam, M. H.
W.; Wong, W.-Y. Inorg. Chem. 2004, 43, 8387–8393.
For the UV–vis absorption titration experiments, typically a
methanol solution of Zn1 or Zn2 was prepared at a fixed