Skip to main content
SpringerLink
Log in

Photorelease of carboxylic and amino acids from N-methyl-4-picolinium esters by mediated electron transfer

  • Paper
  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

One electron reduction of N-alkyl-4-picolinium (NAP) esters initiates C-O bond scission releasing a carboxylate anion. Previous experiments have demonstrated that this process can be initiated by photoinduced electron transfer from an electron-donating sensitizer. In the present study it is demonstrated that a comparable photorelease process can be initiated by photolysis of an electron acceptor (mediator), which in turn abstracts an electron from a ground state electron donor. The resulting mediator anion radicals donate an electron to the NAP ester, triggering release of the carboxylate anion. It is demonstrated that when benzophenone is used as a mediator, higher quantum yields for ester decomposition can be achieved compared with sensitizers that do direct photoinduced electron transfer.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. M. C. Pirrung, L. Fallon and G. McGall, Proofing of photolithographic DNA synthesis with 3′,5′-dimethoxybenzoincarbonyl-protected deoxynucleoside phosphoramidites, J. Org. Chem., 1998, 63, 241–246.

    Article  CAS  Google Scholar 

  2. M. C. Pirrung, W. H. Pieper, K. P. Kaliappan and M. R. Dhananjeyan, Combinatorial discovery of two-photon photoremovable protecting groups, Proc. Natl. Acad. Sci. U. S. A., 2003, 100, 12548–12553.

    Article  CAS  Google Scholar 

  3. G. Marriot and J. W. Walker, Caged peptides and proteins: New probes to study polypeptide function in complex biological systems, Trends Plant Sci., 1999, 4, 330–334.

    Article  Google Scholar 

  4. A. Heckel and G. Mayer, Light regulation of aptamer activity: An anti-thrombin aptamer with caged thymidine nucleobases, J. Am. Chem. Soc., 2005, 127, 822–823.

    Article  CAS  Google Scholar 

  5. V. N. R. Pillai, Photoremovable protecting groups in organic synthesis, Synthesis, 1980, 1–26.

    Google Scholar 

  6. Y. V. Il’ichev, M. A. Schworer and J. Wirz, Photochemical reaction mechanisms of 2-nitrobenzyl compounds: Methyl ethers and caged ATP, J. Am. Chem. Soc., 2004, 126, 4581–4595.

    Article  Google Scholar 

  7. C. Grewer, J. Jager, B. K. Carpenter and G. P. Hess, A new photolabile precursor of glycine with improved properties: A tool for chemical kinetic investigations of the glycine receptor, Biochemistry, 2000, 39, 2063–2070.

    Article  CAS  Google Scholar 

  8. J. Literak, J. Wirz and P. Klan, 2,5-Dimethylphenacyl carbonates: A photoremovable protecting group for alcohols and phenols, Photochem. Photobiol. Sci., 2005, 4, 43–46.

    Article  CAS  Google Scholar 

  9. P. Klán, A. P. Pelliccioli, T. Pospisil and J. Wirz, 2,5-Dimethylphenacyl esters: A photoremovable protecting group for phosphates and sulfonic acids, Photochem. Photobiol. Sci., 2002, 1, 920–923.

    Article  Google Scholar 

  10. R. S. Rock and S. I. Chan, Preparation of a water-soluble “cage” based on 3′,5′-dimethoxybenzoin, J. Am. Chem. Soc., 1998, 120, 10766–10767.

    Article  CAS  Google Scholar 

  11. C. S. Rajesh, R. S. Givens and J. Wirz, Kinetics and mechanism of phosphate photorelease from benzoin diethyl phosphate: Evidence for adiabatic fission to an α-keto cation in the triplet state, J. Am. Chem. Soc., 2000, 122, 611–618.

    Article  CAS  Google Scholar 

  12. R. S. Givens, A. Jung, C.-H. Park, J. Weber and W. Bartlett, New photoactivated protecting groups. 7. p-hydroxyphenacyl: A phototrigger for excitatory amino acids and peptides, J. Am. Chem. Soc., 1997, 119, 8369–8370.

    Article  CAS  Google Scholar 

  13. R. S. Givens, J. F. W. Weber, P. G. Conrad, G. Orosz, S. L. Donahue and S. A. Thayer, New phototriggers 9: p-Hydroxyphenacyl as a C-terminal photoremovable protecting group for oligopeptides, J. Am. Chem. Soc., 2000, 122, 2687–2697.

    Article  CAS  Google Scholar 

  14. T. Furuta, H. Torigai, M. Sugimoto and M. Iwamura, Photochemical properties of new photolabile cAMP derivatives in a physiological saline solution, J. Org. Chem., 1995, 60, 3953–3956.

    Article  CAS  Google Scholar 

  15. T. Furuta, S. S.-H. Wang, J. L. Dantzker, T. Dore, E. J. Bybee, E. M. Callaway, W. Denk and R. Y. Tsien, Brominated 7-hydroxycoumarin-ylmethyls: Photolabile protecting groups with useful cross-sections for two-photon photolysis, Proc. Natl. Acad. Sci. U. S. A., 1999, 96, 1193–2000.

    Article  CAS  Google Scholar 

  16. G. Papageorgiou, D. C. Ogden, A. Barth and J. E. T. Corrie, Photorelease of carboxylic acids from 1-acyl-7-nitroindolines in aqueous solution: Rapid and efficient photorelease of l-glutamate, J. Am. Chem. Soc., 1999, 121, 6503–6504.

    Article  CAS  Google Scholar 

  17. M. Canepari, L. Nelson, G. Papageorgiou, J. E. T. Corrie and D. C. Ogden, Photochemical and pharmacological evaluation of 7-nitroindolinyl- and 4-methoxy-7-nitroindolinyl-amino acids as novel, fast caged neurotransmitters, J. Neurosci. Methods, 2001, 112, 29–42.

    Article  CAS  Google Scholar 

  18. Z. Li, Y. Wan and A. G. Kutateladze, Dithiane-based photolabile amphiphiles: Toward photolabile liposomes, Langmuir, 2003, 19, 6381–6391.

    Article  CAS  Google Scholar 

  19. T. Hamada, A. Nishida and O. Yonemitsu, A new amino protecting group readily removable with near ultraviolet light as an application of electron-transfer photochemistry, Tetrahedron Lett., 1989, 30, 4241–4244.

    Article  CAS  Google Scholar 

  20. G. Papageorgiou, D. C. Ogden and J. E. T. Corrie, An antenna-sensitized nitroindoline precursor to enable photorelease of l-glutamate in high concentrations, J. Org. Chem., 2004, 69, 7228–7233.

    Article  CAS  Google Scholar 

  21. G. Papageorgiou, M. Lukeman, P. Wan and J. E. T. Corrie, An antenna triplet sensitiser for 1-acyl-7-nitroindolines improves the efficiency of carboxylic acid photorelease, Photochem. Photobiol. Sci., 2004, 3, 366–373.

    Article  CAS  Google Scholar 

  22. A. Banerjee and D. E. Falvey, Protecting groups that can be released through photoinduced electron transfer: Mechanistic and product studies of photosensitized release of carboxylates from phenacyl esters, J. Org. Chem., 1997, 62, 6245–6251.

    Article  CAS  Google Scholar 

  23. C. Sundararajan and D. E. Falvey, C-O bond fragmentation of 4-picolyl and N-methyl-4-picolinium esters triggered by photochemical electron transfer, J. Org. Chem., 2004, 69, 5547–5554.

    Article  CAS  Google Scholar 

  24. C. Sundararajan and D. E. Falvey, Photorelease of carboxylic acids, amino acids, and phosphates from N-alkylpicolinium esters using photosensitization by high wavelength laser dyes, J. Am. Chem. Soc., 2005, 127, 8000–8001.

    Article  CAS  Google Scholar 

  25. C. Sundararajan and D. E. Falvey, Photolytic release of carboxylic acids using linked donor-acceptor molecules: Direct versus mediated photoinduced electron transfer to N-alkyl-4-picolinium esters, Org. Lett., 2005, 7, 2631–2634.

    Article  CAS  Google Scholar 

  26. T. L. Morkin, N. J. Turro, M. H. Kleinman, C. S. Brindle, W. H. Kramer and I. R. Gould, Selective solid state photooxidant, J. Am. Chem. Soc., 2003, 125, 14917–14924.

    Article  CAS  Google Scholar 

  27. H. Rinderhagen and J. Mattay, Cyclopropyl silyl ether radical cations. Part 1: Synthetic applications in radical/radical cationic cascade reactions, Chem.-Eur. J., 2004, 10, 851–874.

    Article  CAS  Google Scholar 

  28. S. L. Murov, I. Carmichael, and G. L. Hug, Handbook of photochemistry, Marcel Dekker Inc., New York, 2nd edn, 1993.

    Google Scholar 

  29. A. J. Bard, K. S. V. Santhanam, J. T. Maloy, J. Phelps and L. O. Wheeler, Steric effects and the electrochemistry of phenyl-substituted anthracenes and related compounds, Discuss. Faraday Soc., 1968, 45, 167–174.

    Article  Google Scholar 

  30. T. Shida, Electronic absorption spectra of radical ions, Elsevier, Amsterdam, 1988.

    Google Scholar 

  31. M. Goez and B. H. M. Hussien, Photoionization of xanthone via its triplet state or via its radical anion, Phys. Chem. Chem. Phys., 2004, 6(24), 5490–5497.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, 20742-2021, USA

    Chitra Sundararajan & Daniel E. Falvey

Authors
  1. Chitra Sundararajan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Daniel E. Falvey
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Daniel E. Falvey.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Sundararajan, C., Falvey, D.E. Photorelease of carboxylic and amino acids from N-methyl-4-picolinium esters by mediated electron transfer. Photochem Photobiol Sci 5, 116–121 (2006). https://doi.org/10.1039/b511269a

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/b511269a

Search

Navigation