Model systems for flavoenzyme activity. Specific hydrogen bond recognition of flavin in a silicate sol-gel

Journal of the American Chemical Society

Volumn 119, Issue 44, 1997, Pages 10569-10572

  Greaves, Michael D ^a   Rotello, Vincent M ^a  

^a UNIVERSITY OF MASSACHUSETTS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

FLAVOPROTEIN; QUERCETIN; SILICATE;

ARTICLE; ENZYME ACTIVE SITE; ENZYME ACTIVITY; GEL; HYDROGEN BOND; MODEL;

EID: 0030838307     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja971175k     Document Type: Article

References (72)

1. Gallo, E.; Gellman, S. J. Am. Chem, Soc. 1993, 115, 9774-9788. Zimmerman, S.; Murray, T. Tetrahedron Lett. 1994, 4077-4080. Nowick, J.; Chen, J.; Noronha, G. J. Am. Chem. Soc. 1993, 115, 7636-7644. Das, G.; Hamilton, A. J. Am. Chem. Soc. 1994, 116, 11139.
2. Gallo, E.; Gellman, S. J. Am. Chem, Soc. 1993, 115, 9774-9788. Zimmerman, S.; Murray, T. Tetrahedron Lett. 1994, 4077-4080. Nowick, J.; Chen, J.; Noronha, G. J. Am. Chem. Soc. 1993, 115, 7636-7644. Das, G.; Hamilton, A. J. Am. Chem. Soc. 1994, 116, 11139.
3. Gallo, E.; Gellman, S. J. Am. Chem, Soc. 1993, 115, 9774-9788. Zimmerman, S.; Murray, T. Tetrahedron Lett. 1994, 4077-4080. Nowick, J.; Chen, J.; Noronha, G. J. Am. Chem. Soc. 1993, 115, 7636-7644. Das, G.; Hamilton, A. J. Am. Chem. Soc. 1994, 116, 11139.
4. Gallo, E.; Gellman, S. J. Am. Chem, Soc. 1993, 115, 9774-9788. Zimmerman, S.; Murray, T. Tetrahedron Lett. 1994, 4077-4080. Nowick, J.; Chen, J.; Noronha, G. J. Am. Chem. Soc. 1993, 115, 7636-7644. Das, G.; Hamilton, A. J. Am. Chem. Soc. 1994, 116, 11139.
5. Cram, D. J. Nature, 1992, 356, 29. Cram, D. J.; Jaeger, R.; Deshayes, K. J. Am. Chem. Soc. 1993, 115, 10111. Breslow, R. Acc. Chem. Res. 1995, 28, 146. Branda, N.; Wyeler, R.; Rebek, J. Science, 1994, 263, 1222. For an example of molecular imprinting see: Morihara, K.; Kurihara, S.; Suzuki, J. Bull. Chem. Soc. Jpn. 1988, 61, 3991.
6. Cram, D. J. Nature, 1992, 356, 29. Cram, D. J.; Jaeger, R.; Deshayes, K. J. Am. Chem. Soc. 1993, 115, 10111. Breslow, R. Acc. Chem. Res. 1995, 28, 146. Branda, N.; Wyeler, R.; Rebek, J. Science, 1994, 263, 1222. For an example of molecular imprinting see: Morihara, K.; Kurihara, S.; Suzuki, J. Bull. Chem. Soc. Jpn. 1988, 61, 3991.
7. Cram, D. J. Nature, 1992, 356, 29. Cram, D. J.; Jaeger, R.; Deshayes, K. J. Am. Chem. Soc. 1993, 115, 10111. Breslow, R. Acc. Chem. Res. 1995, 28, 146. Branda, N.; Wyeler, R.; Rebek, J. Science, 1994, 263, 1222. For an example of molecular imprinting see: Morihara, K.; Kurihara, S.; Suzuki, J. Bull. Chem. Soc. Jpn. 1988, 61, 3991.
8. Cram, D. J. Nature, 1992, 356, 29. Cram, D. J.; Jaeger, R.; Deshayes, K. J. Am. Chem. Soc. 1993, 115, 10111. Breslow, R. Acc. Chem. Res. 1995, 28, 146. Branda, N.; Wyeler, R.; Rebek, J. Science, 1994, 263, 1222. For an example of molecular imprinting see: Morihara, K.; Kurihara, S.; Suzuki, J. Bull. Chem. Soc. Jpn. 1988, 61, 3991.
9. Cram, D. J. Nature, 1992, 356, 29. Cram, D. J.; Jaeger, R.; Deshayes, K. J. Am. Chem. Soc. 1993, 115, 10111. Breslow, R. Acc. Chem. Res. 1995, 28, 146. Branda, N.; Wyeler, R.; Rebek, J. Science, 1994, 263, 1222. For an example of molecular imprinting see: Morihara, K.; Kurihara, S.; Suzuki, J. Bull. Chem. Soc. Jpn. 1988, 61, 3991.
10. (a) Breinlinger, E.; Rotello, V. J. Am. Chem. Soc. 1997, 119, 1165.
11. (b) Deans, R.; Rotello, V. Tetrahedron Lett. 1996, 4435-4438.
12. (c) Lambert, T.; Breinlinger, E.; Rotello, V. J. Org. Chem. 1995, 60, 2646-2647.
13. (d) Breinlinger, E.; Niemz, A.; Rotello, V. J. Am. Chem. Soc. 1995, 117, 5379-5380.
14. For reviews of the chemistry and biochemistry of flavoproteins see: Walsh, C. Enzymatic Reaction Mechanisms; W. H. Freeman: New York, 1979; pp 358-521. Walsh, C. Acc. Chem. Res. 1980, 13, 148-155. Müller, F. Top. Curr. Chem. 1983, 108, 71-109. Ziegler, D. M. Trends Pharmacol. Sci. 1990, 321-324. Müller, F., Ed. Chemistry and Biochemistry of the Flavoenzymes; CRC: Boca Raton, 1992; Vol. III.
15. For reviews of the chemistry and biochemistry of flavoproteins see: Walsh, C. Enzymatic Reaction Mechanisms; W. H. Freeman: New York, 1979; pp 358-521. Walsh, C. Acc. Chem. Res. 1980, 13, 148-155. Müller, F. Top. Curr. Chem. 1983, 108, 71-109. Ziegler, D. M. Trends Pharmacol. Sci. 1990, 321-324. Müller, F., Ed. Chemistry and Biochemistry of the Flavoenzymes; CRC: Boca Raton, 1992; Vol. III.
16. For reviews of the chemistry and biochemistry of flavoproteins see: Walsh, C. Enzymatic Reaction Mechanisms; W. H. Freeman: New York, 1979; pp 358-521. Walsh, C. Acc. Chem. Res. 1980, 13, 148-155. Müller, F. Top. Curr. Chem. 1983, 108, 71-109. Ziegler, D. M. Trends Pharmacol. Sci. 1990, 321-324. Müller, F., Ed. Chemistry and Biochemistry of the Flavoenzymes; CRC: Boca Raton, 1992; Vol. III.
17. For reviews of the chemistry and biochemistry of flavoproteins see: Walsh, C. Enzymatic Reaction Mechanisms; W. H. Freeman: New York, 1979; pp 358-521. Walsh, C. Acc. Chem. Res. 1980, 13, 148-155. Müller, F. Top. Curr. Chem. 1983, 108, 71-109. Ziegler, D. M. Trends Pharmacol. Sci. 1990, 321-324. Müller, F., Ed. Chemistry and Biochemistry of the Flavoenzymes; CRC: Boca Raton, 1992; Vol. III.
18. For reviews of the chemistry and biochemistry of flavoproteins see: Walsh, C. Enzymatic Reaction Mechanisms; W. H. Freeman: New York, 1979; pp 358-521. Walsh, C. Acc. Chem. Res. 1980, 13, 148-155. Müller, F. Top. Curr. Chem. 1983, 108, 71-109. Ziegler, D. M. Trends Pharmacol. Sci. 1990, 321-324. Müller, F., Ed. Chemistry and Biochemistry of the Flavoenzymes; CRC: Boca Raton, 1992; Vol. III.
19. For previously published model systems for flavoenzymes see: (a) Shinkai, S.; Ishikawa, Y.; Shinkai, H.; Tsuno, T.; Makishima, H.; Ueda, K.; Manabe, O. J. Am. Chem. Soc. 1984, 106, 1801-1808. (b) Tabushi, I.; Kodera, M. J. Am. Chem. Soc. 1987, 109, 4734-4735. (c) Akiyama, T.; Simeno, F.; Murakami, M.; Yoneda, F. J. Am. Chem. Soc. 1992, 114, 6613-6620. (d) Seward, E. M.; Hopkins, R. B.; Sauerer, W.; Tam, S.-W.; Diederich, F. J. Am. Chem. Soc. 1987, 102, 1783-1790. (e) Hasford, J.; Kemnitzer, W.; Rizzo, C J. Org. Chem. 1997, 62, 5244.
20. For previously published model systems for flavoenzymes see: (a) Shinkai, S.; Ishikawa, Y.; Shinkai, H.; Tsuno, T.; Makishima, H.; Ueda, K.; Manabe, O. J. Am. Chem. Soc. 1984, 106, 1801-1808. (b) Tabushi, I.; Kodera, M. J. Am. Chem. Soc. 1987, 109, 4734-4735. (c) Akiyama, T.; Simeno, F.; Murakami, M.; Yoneda, F. J. Am. Chem. Soc. 1992, 114, 6613-6620. (d) Seward, E. M.; Hopkins, R. B.; Sauerer, W.; Tam, S.-W.; Diederich, F. J. Am. Chem. Soc. 1987, 102, 1783-1790. (e) Hasford, J.; Kemnitzer, W.; Rizzo, C J. Org. Chem. 1997, 62, 5244.
21. For previously published model systems for flavoenzymes see: (a) Shinkai, S.; Ishikawa, Y.; Shinkai, H.; Tsuno, T.; Makishima, H.; Ueda, K.; Manabe, O. J. Am. Chem. Soc. 1984, 106, 1801-1808. (b) Tabushi, I.; Kodera, M. J. Am. Chem. Soc. 1987, 109, 4734-4735. (c) Akiyama, T.; Simeno, F.; Murakami, M.; Yoneda, F. J. Am. Chem. Soc. 1992, 114, 6613-6620. (d) Seward, E. M.; Hopkins, R. B.; Sauerer, W.; Tam, S.-W.; Diederich, F. J. Am. Chem. Soc. 1987, 102, 1783-1790. (e) Hasford, J.; Kemnitzer, W.; Rizzo, C J. Org. Chem. 1997, 62, 5244.
22. For previously published model systems for flavoenzymes see: (a) Shinkai, S.; Ishikawa, Y.; Shinkai, H.; Tsuno, T.; Makishima, H.; Ueda, K.; Manabe, O. J. Am. Chem. Soc. 1984, 106, 1801-1808. (b) Tabushi, I.; Kodera, M. J. Am. Chem. Soc. 1987, 109, 4734-4735. (c) Akiyama, T.; Simeno, F.; Murakami, M.; Yoneda, F. J. Am. Chem. Soc. 1992, 114, 6613-6620. (d) Seward, E. M.; Hopkins, R. B.; Sauerer, W.; Tam, S.-W.; Diederich, F. J. Am. Chem. Soc. 1987, 102, 1783-1790. (e) Hasford, J.; Kemnitzer, W.; Rizzo, C J. Org. Chem. 1997, 62, 5244.
23. For previously published model systems for flavoenzymes see: (a) Shinkai, S.; Ishikawa, Y.; Shinkai, H.; Tsuno, T.; Makishima, H.; Ueda, K.; Manabe, O. J. Am. Chem. Soc. 1984, 106, 1801-1808. (b) Tabushi, I.; Kodera, M. J. Am. Chem. Soc. 1987, 109, 4734-4735. (c) Akiyama, T.; Simeno, F.; Murakami, M.; Yoneda, F. J. Am. Chem. Soc. 1992, 114, 6613-6620. (d) Seward, E. M.; Hopkins, R. B.; Sauerer, W.; Tam, S.-W.; Diederich, F. J. Am. Chem. Soc. 1987, 102, 1783-1790. (e) Hasford, J.; Kemnitzer, W.; Rizzo, C J. Org. Chem. 1997, 62, 5244.
24. For sernisynthetic, protein-based systems see: (a) Levine, H. L.; Kaiser, E. T. J. Am. Chem. Soc. 1978, 100, 7670-7677. (b) Schultz, P. G. Acc. Chem. Res. 1989, 22, 287-294.
25. For sernisynthetic, protein-based systems see: (a) Levine, H. L.; Kaiser, E. T. J. Am. Chem. Soc. 1978, 100, 7670-7677. (b) Schultz, P. G. Acc. Chem. Res. 1989, 22, 287-294.
26. For a detailed review of the fundamentals of sol-gel technology see: (a) Brinker, C. J.; Scherer, G. W. Sol-Gel Science, Academic Press: San Diego, 1990. (b) Hench, L.; West, J. Chem. Rev. 1990, 90, 33-72. (c) Buckley, A. M.; Greenblatt, M. J. Chem. Educ. 1994, 71, 599-602.
27. For a detailed review of the fundamentals of sol-gel technology see: (a) Brinker, C. J.; Scherer, G. W. Sol-Gel Science, Academic Press: San Diego, 1990. (b) Hench, L.; West, J. Chem. Rev. 1990, 90, 33-72. (c) Buckley, A. M.; Greenblatt, M. J. Chem. Educ. 1994, 71, 599-602.
28. For a detailed review of the fundamentals of sol-gel technology see: (a) Brinker, C. J.; Scherer, G. W. Sol-Gel Science, Academic Press: San Diego, 1990. (b) Hench, L.; West, J. Chem. Rev. 1990, 90, 33-72. (c) Buckley, A. M.; Greenblatt, M. J. Chem. Educ. 1994, 71, 599-602.
29. Narang, U.; Bright, F. V.; Prasad, P. N. Appl. Spectrosc. 1993, 47, 229-234. Nishida, F.; McKiernan, J. M.; Dunn, B.; Zink, J. I.; Brinker, C. J.; Hurd, A. J. Am. Ceram. Soc. 1995, 78, 1640-1648.
30. Narang, U.; Bright, F. V.; Prasad, P. N. Appl. Spectrosc. 1993, 47, 229-234. Nishida, F.; McKiernan, J. M.; Dunn, B.; Zink, J. I.; Brinker, C. J.; Hurd, A. J. Am. Ceram. Soc. 1995, 78, 1640-1648.
31. Kurokawa, Y.; Sano, T.; Ohta, H.; Nakagawa, Y. Biotechnol. Bioeng. 1993, 42, 394.
32. Rao, A.; Pajonk, G.; Parvathy, N.; Elaloui, E. in Sol-Gel Processing and Applications; Attia, Y., Ed.; Plenum: New York, 1994; pp 237-256. Hrubesh, L. W.; Pekala, R. W. Sol-Gel Processing and Applications; Attia, Y., Ed.; Plenum: New York, 1994; pp 363-377. Narang, U.; Rahman, M. H.; Wang, J. H.; Prasad, P. N.; Bright, F. V. Anal. Chem. 1995, 67, 1935-1939. Laperriere, S. C.; Mullens, J. W.; L'Esperance, D.; Chronister, E. L. Chem. Phys. Lett. 1995, 243, 114-124.
33. Rao, A.; Pajonk, G.; Parvathy, N.; Elaloui, E. in Sol-Gel Processing and Applications; Attia, Y., Ed.; Plenum: New York, 1994; pp 237-256. Hrubesh, L. W.; Pekala, R. W. Sol-Gel Processing and Applications; Attia, Y., Ed.; Plenum: New York, 1994; pp 363-377. Narang, U.; Rahman, M. H.; Wang, J. H.; Prasad, P. N.; Bright, F. V. Anal. Chem. 1995, 67, 1935-1939. Laperriere, S. C.; Mullens, J. W.; L'Esperance, D.; Chronister, E. L. Chem. Phys. Lett. 1995, 243, 114-124.
34. Rao, A.; Pajonk, G.; Parvathy, N.; Elaloui, E. in Sol-Gel Processing and Applications; Attia, Y., Ed.; Plenum: New York, 1994; pp 237-256. Hrubesh, L. W.; Pekala, R. W. Sol-Gel Processing and Applications; Attia, Y., Ed.; Plenum: New York, 1994; pp 363-377. Narang, U.; Rahman, M. H.; Wang, J. H.; Prasad, P. N.; Bright, F. V. Anal. Chem. 1995, 67, 1935-1939. Laperriere, S. C.; Mullens, J. W.; L'Esperance, D.; Chronister, E. L. Chem. Phys. Lett. 1995, 243, 114-124.
35. Rao, A.; Pajonk, G.; Parvathy, N.; Elaloui, E. in Sol-Gel Processing and Applications; Attia, Y., Ed.; Plenum: New York, 1994; pp 237-256. Hrubesh, L. W.; Pekala, R. W. Sol-Gel Processing and Applications; Attia, Y., Ed.; Plenum: New York, 1994; pp 363-377. Narang, U.; Rahman, M. H.; Wang, J. H.; Prasad, P. N.; Bright, F. V. Anal. Chem. 1995, 67, 1935-1939. Laperriere, S. C.; Mullens, J. W.; L'Esperance, D.; Chronister, E. L. Chem. Phys. Lett. 1995, 243, 114-124.
36. Parish, K. Y.; Habibi, D.; Mohammadi, V. J. Organomet. Chem. 1989, 369, 17. Slama-Schwok, A.; Avnir, D.; Ottolenghi, M. J. Am. Chem. Soc. 1991, 113, 3984. Rosenfeld, A.; Avnir, D.; Blum, J. J. Chem. Soc., Chem. Commun. 1993, 583.
37. Parish, K. Y.; Habibi, D.; Mohammadi, V. J. Organomet. Chem. 1989, 369, 17. Slama-Schwok, A.; Avnir, D.; Ottolenghi, M. J. Am. Chem. Soc. 1991, 113, 3984. Rosenfeld, A.; Avnir, D.; Blum, J. J. Chem. Soc., Chem. Commun. 1993, 583.
38. Parish, K. Y.; Habibi, D.; Mohammadi, V. J. Organomet. Chem. 1989, 369, 17. Slama-Schwok, A.; Avnir, D.; Ottolenghi, M. J. Am. Chem. Soc. 1991, 113, 3984. Rosenfeld, A.; Avnir, D.; Blum, J. J. Chem. Soc., Chem. Commun. 1993, 583.
39. Tani, T.; Namikawa, A.; Arai, K.; Makishima, A. J. Appl. Phys. 1985, 58, 3559. Avnir, D.; Kaufman, V. R.; Reisfeld, R. J. Non-Cryst. Solids 1985, 74, 395. Audebert, P.; Demaille, C.; Sanchez, C. Chem. Mater. 1993, 5, 911-913. Avnir, D.; Braun, S.; Lev, O.; Ottolenghi, M. Chem. Mater. 1994, 6, 1605-1614. For a review of dopants in the sol-gel process see: Avnir, D. Acc. Chem. Res. 1995, 28, 328-334
40. Tani, T.; Namikawa, A.; Arai, K.; Makishima, A. J. Appl. Phys. 1985, 58, 3559. Avnir, D.; Kaufman, V. R.; Reisfeld, R. J. Non-Cryst. Solids 1985, 74, 395. Audebert, P.; Demaille, C.; Sanchez, C. Chem. Mater. 1993, 5, 911-913. Avnir, D.; Braun, S.; Lev, O.; Ottolenghi, M. Chem. Mater. 1994, 6, 1605-1614. For a review of dopants in the sol-gel process see: Avnir, D. Acc. Chem. Res. 1995, 28, 328-334
41. Tani, T.; Namikawa, A.; Arai, K.; Makishima, A. J. Appl. Phys. 1985, 58, 3559. Avnir, D.; Kaufman, V. R.; Reisfeld, R. J. Non-Cryst. Solids 1985, 74, 395. Audebert, P.; Demaille, C.; Sanchez, C. Chem. Mater. 1993, 5, 911-913. Avnir, D.; Braun, S.; Lev, O.; Ottolenghi, M. Chem. Mater. 1994, 6, 1605-1614. For a review of dopants in the sol-gel process see: Avnir, D. Acc. Chem. Res. 1995, 28, 328-334
42. Tani, T.; Namikawa, A.; Arai, K.; Makishima, A. J. Appl. Phys. 1985, 58, 3559. Avnir, D.; Kaufman, V. R.; Reisfeld, R. J. Non-Cryst. Solids 1985, 74, 395. Audebert, P.; Demaille, C.; Sanchez, C. Chem. Mater. 1993, 5, 911-913. Avnir, D.; Braun, S.; Lev, O.; Ottolenghi, M. Chem. Mater. 1994, 6, 1605-1614. For a review of dopants in the sol-gel process see: Avnir, D. Acc. Chem. Res. 1995, 28, 328-334
43. Tani, T.; Namikawa, A.; Arai, K.; Makishima, A. J. Appl. Phys. 1985, 58, 3559. Avnir, D.; Kaufman, V. R.; Reisfeld, R. J. Non-Cryst. Solids 1985, 74, 395. Audebert, P.; Demaille, C.; Sanchez, C. Chem. Mater. 1993, 5, 911-913. Avnir, D.; Braun, S.; Lev, O.; Ottolenghi, M. Chem. Mater. 1994, 6, 1605-1614. For a review of dopants in the sol-gel process see: Avnir, D. Acc. Chem. Res. 1995, 28, 328-334
44. Braun, S.; Shtelzer, S.; Rappoport, S.; Avnir, D.; Ottolenahi, M. J. Non-Cryst. Solids, 1992, 147 & 148, 739. Ellerby, L. M.; Nishida, C. R.; Nishida, F.; Yamanaka, S. A.; Dunn, B.; Valentine, J. S.; Zink, J. I. Science, 1992, 255, 1113-1115. Shtelzer, S.; Braun, S. Biotechnol. Appl. Biochem. 1994, 19, 293.
45. Braun, S.; Shtelzer, S.; Rappoport, S.; Avnir, D.; Ottolenahi, M. J. Non-Cryst. Solids, 1992, 147 & 148, 739. Ellerby, L. M.; Nishida, C. R.; Nishida, F.; Yamanaka, S. A.; Dunn, B.; Valentine, J. S.; Zink, J. I. Science, 1992, 255, 1113-1115. Shtelzer, S.; Braun, S. Biotechnol. Appl. Biochem. 1994, 19, 293.
46. Braun, S.; Shtelzer, S.; Rappoport, S.; Avnir, D.; Ottolenahi, M. J. Non-Cryst. Solids, 1992, 147 & 148, 739. Ellerby, L. M.; Nishida, C. R.; Nishida, F.; Yamanaka, S. A.; Dunn, B.; Valentine, J. S.; Zink, J. I. Science, 1992, 255, 1113-1115. Shtelzer, S.; Braun, S. Biotechnol. Appl. Biochem. 1994, 19, 293.
47. For examples of use of sol-gel encapsulated biomolecules as biosensors see: (a) Braun, S.; Rappoport, S.; Zusman, R.; Avnir, D.; Ottolenghi, M. Mater. Lett. 1990, 10, 1. (b) Yamanaka, S. A.; Dunn, B.; Valentine, J. S.; Zink, J. I. J. Am. Chem. Soc. 1995, 117, 9095-9096. (c) Chen, Z.; Samuelson, J. A.; Kaplan, D. L.; Gao, H.; Kumar, J.; Marx, K. A.; Tripathy, S. K. Chem. Mater. 1995, 7, 1779-1783. (d) Pankratov, I.; Lev, O. J. Electroanal. Chem. 1995, 393, 35-41.
48. For examples of use of sol-gel encapsulated biomolecules as biosensors see: (a) Braun, S.; Rappoport, S.; Zusman, R.; Avnir, D.; Ottolenghi, M. Mater. Lett. 1990, 10, 1. (b) Yamanaka, S. A.; Dunn, B.; Valentine, J. S.; Zink, J. I. J. Am. Chem. Soc. 1995, 117, 9095-9096. (c) Chen, Z.; Samuelson, J. A.; Kaplan, D. L.; Gao, H.; Kumar, J.; Marx, K. A.; Tripathy, S. K. Chem. Mater. 1995, 7, 1779-1783. (d) Pankratov, I.; Lev, O. J. Electroanal. Chem. 1995, 393, 35-41.
49. For examples of use of sol-gel encapsulated biomolecules as biosensors see: (a) Braun, S.; Rappoport, S.; Zusman, R.; Avnir, D.; Ottolenghi, M. Mater. Lett. 1990, 10, 1. (b) Yamanaka, S. A.; Dunn, B.; Valentine, J. S.; Zink, J. I. J. Am. Chem. Soc. 1995, 117, 9095-9096. (c) Chen, Z.; Samuelson, J. A.; Kaplan, D. L.; Gao, H.; Kumar, J.; Marx, K. A.; Tripathy, S. K. Chem. Mater. 1995, 7, 1779-1783. (d) Pankratov, I.; Lev, O. J. Electroanal. Chem. 1995, 393, 35-41.
50. For examples of use of sol-gel encapsulated biomolecules as biosensors see: (a) Braun, S.; Rappoport, S.; Zusman, R.; Avnir, D.; Ottolenghi, M. Mater. Lett. 1990, 10, 1. (b) Yamanaka, S. A.; Dunn, B.; Valentine, J. S.; Zink, J. I. J. Am. Chem. Soc. 1995, 117, 9095-9096. (c) Chen, Z.; Samuelson, J. A.; Kaplan, D. L.; Gao, H.; Kumar, J.; Marx, K. A.; Tripathy, S. K. Chem. Mater. 1995, 7, 1779-1783. (d) Pankratov, I.; Lev, O. J. Electroanal. Chem. 1995, 393, 35-41.
51. Müller, F. In Chemistry and Biochemistry of Flavoenzymes; Müller, F., Ed.; CRC: Ann Arbor, 1992; Vol. III, pp 557-595. Müller, F.; Vervoort, J.; Mierlo, P.; Mayhew, S.; van Berkel, W.; Bacher, A. Flavins and Flavoproteins 1990; Kurti, B., Ronchi, S., Zanetti, G., Ed.; De Gruyter: Berlin, 1991; pp 261-270.
52. Müller, F. In Chemistry and Biochemistry of Flavoenzymes; Müller, F., Ed.; CRC: Ann Arbor, 1992; Vol. III, pp 557-595. Müller, F.; Vervoort, J.; Mierlo, P.; Mayhew, S.; van Berkel, W.; Bacher, A. Flavins and Flavoproteins 1990; Kurti, B., Ronchi, S., Zanetti, G., Ed.; De Gruyter: Berlin, 1991; pp 261-270.
53. The lack of flavin extraction was confirmed via UV/vis and fluorescence spectroscopy.
54. Niemz, A.; Rotello, V. J. Mol. Recognit. 1996, 9, 158.
55. (a) MacKenzie, R. E.; Fory, W.; McCormick, D. B. Biochemistry 1969, 8, 1839-1844.
56. (b) Kouyama, T.; Mihashi, K. Eur. J. Biochem. 1981, 114, 33-38.
57. Koziol, J. Photochem. Photobiol. 1969, 9, 45-53. Yagi, K.; Ohishi, N.; Nishimoto, K.; Choi, J. D.; Song, P-S. Biochemistry 1980, 19, 1553-1557. Heelis, P. Chem Rev. 1982, 11(1), 15-39.
58. Koziol, J. Photochem. Photobiol. 1969, 9, 45-53. Yagi, K.; Ohishi, N.; Nishimoto, K.; Choi, J. D.; Song, P-S. Biochemistry 1980, 19, 1553-1557. Heelis, P. Chem Rev. 1982, 11(1), 15-39.
59. Koziol, J. Photochem. Photobiol. 1969, 9, 45-53. Yagi, K.; Ohishi, N.; Nishimoto, K.; Choi, J. D.; Song, P-S. Biochemistry 1980, 19, 1553-1557. Heelis, P. Chem Rev. 1982, 11(1), 15-39.
60. Tamura, N.; Mitsui, K.; Nabeshima, T.; Yano, Y. J. Chem. Soc., Perkin. Trans. 1994, 2, 2229-2237. For fitting of the binding isotherm see: Deans, R.; Rotello, V. M. J. Org. Chem. 1997, 62, 4528.
61. Tamura, N.; Mitsui, K.; Nabeshima, T.; Yano, Y. J. Chem. Soc., Perkin. Trans. 1994, 2, 2229-2237. For fitting of the binding isotherm see: Deans, R.; Rotello, V. M. J. Org. Chem. 1997, 62, 4528.
62. Addition of higher quantities (>30 equiv) of both receptor 3 and control 4 resulted in a very gradual decrease in fluorescence intensity. This presumably arises from other interactions possible between receptor and flavin, such as π-stacking or nonspecific aggregation. Due to these nonspecific interactions, complete saturation of flavin with receptor 3 could not be achieved.
63. The uncertainty presented is the asymptotic standard error (A.S.E.). The value presented is for comparison purposes, as this system is obviously not in the standard state.
64. Niemz, A.; Rotello, V. J. Am. Chem. Soc. 1997, 119, 887-892.
65. N(10) isobutyl flavin was used for these studies due to the low solubility of FMN in methanol. Since the only difference between this flavin and FMN is in the spatially remote side chain, recognition at the O(2), N(3), and O(4) surface of this flavin is expected to be comparable.
66. For studies probing the microenvironment within sol-gel pores see: Avnir, D.; Levy, D.; Reisfeld, R. J. Phys. Chem. 1984, 88, 5956-5959. McKiernan, J.; Pouxviel, J-C.; Dunn, B.; Zink, J. I. J. Phys. Chem. 1989, 93, 2129-2133. Winter, R.; Hua, D. W.; Song, X.; Mantulin, S. W.; Jonas, J. J. Phys. Chem. 1990, 94, 2706-2713. Matsui, K.; Nakazawa, T.; Morisaki, H. J. Phys. Chem. 1991, 95, 976-979. Narang, U.; Jordan, J. D.; Bright, F. V.; Prasad, P. N. J. Phys. Chem. 1994, 98, 8101-8107. Ilharco, L. M.; Santos, A. M.; Silva, M. J.; Martinho, J. M. G. Langmuir 1995, 11, 2419-2422.
67. For studies probing the microenvironment within sol-gel pores see: Avnir, D.; Levy, D.; Reisfeld, R. J. Phys. Chem. 1984, 88, 5956-5959. McKiernan, J.; Pouxviel, J-C.; Dunn, B.; Zink, J. I. J. Phys. Chem. 1989, 93, 2129-2133. Winter, R.; Hua, D. W.; Song, X.; Mantulin, S. W.; Jonas, J. J. Phys. Chem. 1990, 94, 2706-2713. Matsui, K.; Nakazawa, T.; Morisaki, H. J. Phys. Chem. 1991, 95, 976-979. Narang, U.; Jordan, J. D.; Bright, F. V.; Prasad, P. N. J. Phys. Chem. 1994, 98, 8101-8107. Ilharco, L. M.; Santos, A. M.; Silva, M. J.; Martinho, J. M. G. Langmuir 1995, 11, 2419-2422.
68. For studies probing the microenvironment within sol-gel pores see: Avnir, D.; Levy, D.; Reisfeld, R. J. Phys. Chem. 1984, 88, 5956-5959. McKiernan, J.; Pouxviel, J-C.; Dunn, B.; Zink, J. I. J. Phys. Chem. 1989, 93, 2129-2133. Winter, R.; Hua, D. W.; Song, X.; Mantulin, S. W.; Jonas, J. J. Phys. Chem. 1990, 94, 2706-2713. Matsui, K.; Nakazawa, T.; Morisaki, H. J. Phys. Chem. 1991, 95, 976-979. Narang, U.; Jordan, J. D.; Bright, F. V.; Prasad, P. N. J. Phys. Chem. 1994, 98, 8101-8107. Ilharco, L. M.; Santos, A. M.; Silva, M. J.; Martinho, J. M. G. Langmuir 1995, 11, 2419-2422.
69. For studies probing the microenvironment within sol-gel pores see: Avnir, D.; Levy, D.; Reisfeld, R. J. Phys. Chem. 1984, 88, 5956-5959. McKiernan, J.; Pouxviel, J-C.; Dunn, B.; Zink, J. I. J. Phys. Chem. 1989, 93, 2129-2133. Winter, R.; Hua, D. W.; Song, X.; Mantulin, S. W.; Jonas, J. J. Phys. Chem. 1990, 94, 2706-2713. Matsui, K.; Nakazawa, T.; Morisaki, H. J. Phys. Chem. 1991, 95, 976-979. Narang, U.; Jordan, J. D.; Bright, F. V.; Prasad, P. N. J. Phys. Chem. 1994, 98, 8101-8107. Ilharco, L. M.; Santos, A. M.; Silva, M. J.; Martinho, J. M. G. Langmuir 1995, 11, 2419-2422.
70. For studies probing the microenvironment within sol-gel pores see: Avnir, D.; Levy, D.; Reisfeld, R. J. Phys. Chem. 1984, 88, 5956-5959. McKiernan, J.; Pouxviel, J-C.; Dunn, B.; Zink, J. I. J. Phys. Chem. 1989, 93, 2129-2133. Winter, R.; Hua, D. W.; Song, X.; Mantulin, S. W.; Jonas, J. J. Phys. Chem. 1990, 94, 2706-2713. Matsui, K.; Nakazawa, T.; Morisaki, H. J. Phys. Chem. 1991, 95, 976-979. Narang, U.; Jordan, J. D.; Bright, F. V.; Prasad, P. N. J. Phys. Chem. 1994, 98, 8101-8107. Ilharco, L. M.; Santos, A. M.; Silva, M. J.; Martinho, J. M. G. Langmuir 1995, 11, 2419-2422.
71. For studies probing the microenvironment within sol-gel pores see: Avnir, D.; Levy, D.; Reisfeld, R. J. Phys. Chem. 1984, 88, 5956-5959. McKiernan, J.; Pouxviel, J-C.; Dunn, B.; Zink, J. I. J. Phys. Chem. 1989, 93, 2129-2133. Winter, R.; Hua, D. W.; Song, X.; Mantulin, S. W.; Jonas, J. J. Phys. Chem. 1990, 94, 2706-2713. Matsui, K.; Nakazawa, T.; Morisaki, H. J. Phys. Chem. 1991, 95, 976-979. Narang, U.; Jordan, J. D.; Bright, F. V.; Prasad, P. N. J. Phys. Chem. 1994, 98, 8101-8107. Ilharco, L. M.; Santos, A. M.; Silva, M. J.; Martinho, J. M. G. Langmuir 1995, 11, 2419-2422.
72. While it was possible to diffuse solvents into the silicate monolith, neither receptor 3 nor flavin 1 could be added or removed from the preformed silicate. This is analogous to the flavoenzymes, where the cofactor is strongly bound by the protein.