Synthetic catalytic pores

Journal of the American Chemical Society

Volumn 125, Issue 26, 2003, Pages 7776-7777

  Sakai, Naomi ^a   Sordé, Nathalie ^a   Matile, Stefan ^a  

^a UNIVERSITY OF GENEVA   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

ION CHANNEL;

ARTICLE; CATALYSIS; CATALYST; ELECTRICITY; MEMBRANE POTENTIAL; POLARIZATION; POROSITY;

ALKANESULFONATES; CATALYSIS; KINETICS; LIPID BILAYERS; MEMBRANE POTENTIALS; MEMBRANES, ARTIFICIAL; PHOSPHATIDYLCHOLINES; PYRENES;

EID: 0037527969     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja029845w     Document Type: Article

References (31)

1. Synthetic catalytic pores (SCPs): pores constructed from abiotic scaffolds that catalyze substrate conversion during substrate translocation across the same pore; "synthetic multifunctional pores" (SMPs): pores constructed from abiotic scaffolds with additional function(s); all SCPs are SMPs, but not all SMPs are SCPs.
2. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
3. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
4. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
5. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
6. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
7. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
8. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
9. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
10. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
11. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
12. Catalytic pores have not been reported previously. SMPs with ion channel and catalytic activity: (a) Baumeister, B.; Sakai, N.; Matile, S. Org. Lett. 2001, 3, 4229-4232. (b) Som, A.; Matile, S. Eur. J. Org. Chem. 2002, 3874-3883. (c) Baumeister, B.; Som, A.; Das, G.; Sakai, N.; Vilbois, F.; Gerard, D.; Shahi, S. P.; Matile, S. Helv. Chim. Acta 2002, 85, 2740-2753. (d) Baumeister, B.; Matile, S. Macromolecules 2002, 35, 1549-1555. (e) Som, A.; Sakai, N.; Matile, S. Bioorg. Med. Chem. 2003, 11, 1363-1369. Molecular recognition within pores: (f) Bayley, H.; Cremer, P. S. Nature 2001, 413, 226-230. (g) Das, G.; Talukdar, P.; Matile, S. Science 2002, 298, 1600-1602. Covalent capture within pores: (h) Mindell, J. A.; Zhan, H.; Huynh, P. D.; Collier, R. J.; Finkelstein, A. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 5272-5276. (i) Shin, S.; Luchian, T.; Cheley, S.; Braha, O.; Bayley, H. Angew. Chem., Int. Ed. 2002, 41, 3707-3709. Reactions within vesicles: (j) Walde, P.; Ichikawa, S. Biomol. Eng. 2001, 18, 143-177. Synthetic ion channels/pores: (k) Gokel, G. W.; Mukhopadhyay, A. Chem. Soc. Rev. 2001, 30, 274-286.
13. See Supporting Information
14. Osmotic stress from intravesicular AcPTS was compensated by sucrose. EYPC-LUVs⊃AcPTS, trans catalysis, E = 0 mV: Inside; x mM AcPTS, 100-3.2 x mM sucrose, 100 mM KCl, 5 mM TES, pH 7.0, x = 3-18 mM, outside; 100 mM sucrose, 100 mM KCl, 10 mM MES, pH 5.5. EYPC-LUVs, cis catalysis, E = 0 mV: Inside; 100 mM KCl, 5 mM TES, pH 7.0, outside; 100 mM KCl, 10 mM MES, pH 5.5. For E = -50 mV: NaCl instead of KCl was used for outside buffer in cis and trans esterolysis.
15. "Trans catalysis": addition of substrate (here: intravesicular) and catalyst (here: extravesicular) from opposite sides of the membrane; "cis catalysis": addition of substrate and catalyst from the same side of the membrane (here: extravesicular).
16. (a) Sordé, N.; Matile, S. J. Supramol. Chem. 2003. In press.
17. (b) Sakai, N.; Sordé, N.; Das, G.; Perrottet, P.; Gerard, D.; Matile, S. Org. Biomol. Chem. 2003, 1, 1226-1231.
18. 1 refer to tetramers.
19. 1 (Figure 2A, ii; 50 nM). Concentration of HPTS was determined from HPTS emission intensities using calibration curves.
20. 1 is unknown (Figure 2A, iii). However, clear dependence on substrate concentration suggested that these "bursts" do not originate from accumulation of reactive intermediates.
21. (a) Sakai, N.; Matile, S. J. Am. Chem. Soc. 2002, 124, 1184-1185.
22. (b) Sakai, N.; Houdebert, D.; Matile, S. Chem.-Eur. J. 2003, 9, 223-232.
23. ex = 522 nm) was followed as a function of time simultaneously to the continuous detection of trans AcPTS esterolysis in polarized LUVs (Figure 2A, a). Potentials were quantified from Safranin O emission intensities using calibration curves.
24. Data not shown.
25. 1 at pH 5.5, about 50% initial depolarization is consistent with this explanation.) Decrease of Safranin O emission to the original value for E ≈ 0 mV upon addition of excess melittin confirmed existence of partial polarization (E ≈ -50 mV, Figure 2A, c) during esterolysis (Figure 2Aa).
26. 0 with/without polarization were reproducibly observed in trans catalysis with > 3 μM substrate, measured always in parallel at fixed substrate concentration (Figure 2B, filled versus empty circles).
27. M expected for accelerated efflux, i.e., increased external substrate concentration, upon polarization) and experimental evidence for blockage of cation exchange during 1,3,6-pyrenetrisulfonate efflux. under relevant conditions. (d) Exclusive substrate conversion in the internal media is excluded by the found dependence of trans catalysis on substrate concentration.
28. off of substrate and product to be the same.
29. Electrostatic steering in enzymes, e.g.: Wade, R.; Gabdoulline, R. R.; Lüdemann, S. K.; Lounnas, V. Proc. Natl. Acad. Sci. U.S.A. 1998, 95, 5942-5949.
30. 1) (-56.0 kJ/mol) = +3.8 kJ/mol. Data from 2a.
31. 1 (about 3000x).